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12th Australasian

Organometallics

Meeting

Abstract Book

School of Chemistry,

The University of Melbourne

9th - 12th July 2019

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Table of Contents

Welcome…………………………………………….3

Map of Campus…………………………………….4

Programme………………………………………….5

Plenary Lectures………………………………….12

Keynote Lectures…………………………………16

Special Topic Presentations……………………20

Oral Presentations………………………………..22

Poster Presentations…………………………….56

List of Attendees………………………………….98

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Welcome We welcome you to the 12th Australasian Organometallics Meeting – OZOM12 – back

again in Victoria. In maintaining the previous tradition of these successful

meetings, OZOM12 has its focus on presentations from students and early career

researchers, supported by 4 plenary lectures, 4 keynote lectures and 2 special topic

presentations. The conference covers various aspects of fundamental and applied

organometallic chemistry, including:

• Organometallic chemistry of main, transition, and lanthanoid elements

• Structure and reactivity

• Catalysis

• Asymmetric synthesis

• Theoretical chemistry

• Bio-organometallic chemistry

• Application of organometallic complexes in life science

• Application of organometallic complexes in materials science

• Synthetic chemistry

We thank the School of Chemistry, The University of Melbourne for hosting the

meeting, with lectures being held in the historic Masson Theatre in the School of

Chemistry. We acknowledge the generous support of our sponsors, listed on page 11.

We hope you enjoy yourselves.

The OZOM12 organizing committee:

Richard O’Hair, Chair

Vicki Blair, Treasurer

Carol Hua

Melissa Werrett

Paul Donnelly

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12th Australasian Organometallics Meeting

Programme (OZOM12)

Tuesday 9th July 2019

Registration 15:00 – 17:00

17:00 Opening Address

17:10 Plenary 1 | Penelope Brothers | The chemistry of boron with pyrrole ligands:

tales from the world of porphyrins, corroles, phthalocyanines and BODIPY

Chair: Victoria Blair

18:00 BBQ and Drinks

Wednesday 10th July 2019

9:00 Plenary 2 | Frank Edelmann | My 40-year organometallic journey through the

Periodic Table with frequent stops at the rare-earth elements

Chair: Carol Hua

Session Chair: Ben Frogley

9:50 Alasdair McKay | A Mechanistically Guided Approach to C-H Bond Amidation

10:10 Daven Foster | In-depth study of a Highly Efficient Enantioselective

Intramolecular Hydroamination Reaction

10:30 Morning Tea

11:00 Keynote 1 | Melissa Werrett | Bismuth Nanocellulose Composites and their

Efficacy Towards Multi-Drug Resistant Bacteria

Session Chair: Koushik Venkatesan

11:30 Isabelle Dixon | Theoretical insights into ligand photorelease mechanisms: new

types of 3MC states

11:50 Harrison Barnett | Detection and Reactivity of a Bridging C1 Ligand

12:10 Angus Gillespie | Synthesis and Properties of 2,7-alkynyldihydropyrene

Photochromic Switches

12:30 Lunch Break

13:30 Keynote 2 | Rebecca Fuller | A tale of two cities: Electrostatic potentials are a

chemists best friend and new beginnings with trigonal lanthanoid magnets

Session Chair: Stacey Rudd

14:00 Jamie Greer | Accessing unsupported magnesium 2-aza allyl complexes

14:20 Lynn Lisboa | Switchable Heterometallic Supramolecular Cages

14:40 Albert Paparo | Beryllium

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15:00 Frédéric Paul | Porphyrins and Electron-Rich Alkynyl Complexes: A Step toward

Remarkable Redox-active Molecular Arrays for Electronics or Photonics

15:20 Michael Stevens | Extending Alkali Metal Mediated Magnesiation from nitrogen

to phosphorus

15:40 Afternoon Tea

Session Chair: Marcus Korb

16:10 Samantha Orr | Sodium-magnesiate facilitated cyclisation of imines via C-F bond

activation

16:30 Alphonsine Ngo Ndimba | Tris(styryl)isocyanurates: Towards New Dyes with

Large Two-Photon Absorption Cross-Sections

16:50 Jamie Hicks | Nucleophilic aluminium: Synthesis, structural and reaction

chemistry of the aluminyl anion

17:10 Angus Shephard | New aluminium lanthanoid biphenolate complexes through

redox transmetallation protolysis

17:30 Jeremy Stone | Synthesis of ruthenium diimine complexes for catalysis

Lightning Talk Chair: Albert Paparo

17:50 Lightning Talk 1 | James Findlay

17:55 Lightning Talk 2 | Curtis Ho

18:00 Lightning Talk 3 | Mahbod Morshedi

18:05 Lightning Talk 4 | Rachel Steen

18:10 Lightning Talk 5 | Kuppusamy Yuvaraj

18:15 Lightning Talk 6 | Linda Zhang

18:20 Poster Session

Thursday 11th July 2019

9:00 Plenary 3 | Monica Perez-Temprano | Synergistic Cooperation between

Mechanistic Investigations and Catalysis: Towards Rational Design

Chair: Melissa Werrett

Session Chair: William Erb

9:50 Kirralee Burke | Exploring properties of novel Ga(III) and Bi(III) flavonolate

complexes

10:10 Howard Ma | Caught at Last! Isolation, Structural Characterization and Gas-

phase Studies of the [Ag10(H)8L6]2+ Nanocluster Dication

10:30 Morning Tea

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11:00 Keynote 3 | Nick Cox | High-Field Pulse EPR: A New Biophysical Toolbox for

the Study of Metalloenzymes

Session Chair: Alasdair McKay

11:30 Margaret Aulsebrook | From Reactor to Radiotracer at ANSTO - Increasing the

Availability of Non-routine Radionuclides

11:50 Max Roemer | Robust and Recyclable Hybrid Rhodium- and Iridium-Catalysts

with Long Alkyl Tethers

12:10 Sarmishta Munuganti | An Exploration into the synthesis and microbial activity

of some heterocyclic bismuth-based complexes

12:30 Lunch Break

Special workshop for ECRs | Professors Lou Rendina, Mark Humphrey, Paul

Low | The ARC assessment process

13:30 Keynote 4 | Annie Colebatch | Main Group Pyridyl Ligands: From the Molecular

to the Supramolecular

Session Chair: Fred Paul

14:00 Matthew Gyton | A convenient method for the generation of [Rh(PNP)]+ and

[Rh(PONOP)]+ fragments: reversible formation of vinylidene derivatives

14:20 Benjamin Frogley | Heteroatom-Bridged Transition-Metal Carbynes

14:40 Angelo Frei | Multifunctional Cyclopentadiene Ligands for Theranostic

Approaches with Re and 99mTc

15:00 Sinead Keaveney | Palladium-Catalyzed Decarbonylative Trifluoromethylation of

Acid Fluorides

15:20 Mohammad Al Bayer | Synthesis of difluorogold(III) complexes supported by

N-ligands

15:40 Afternoon Tea

Session Chair: Isabelle Dixon

16:10 Nimrod Eren | Insights into the s-Block Metalations of Allylic Phosphines and

Phosphine Oxides

16:30 Rebekah Duffin | Anti-Leishmanial Activity of Organometallic Antimony (V) And

Gallium (III) Quinolinolato Complexes

16:50 Robert Malmberg | Tunable Photoluminescent Properties of a New Class of

Thermally Robust Monocyclometalated Gold(III) Complexes

17:10 Marcus Korb | Reactions of Planar-Chiral 1-P(S)Ph2-2-CH2OH Ferrocenes

17:30 Special Topic 1 | Ian Rae | Nineteenth Century Organometallics in Melbourne

Chair: Richard O’Hair

19:00 Conference Dinner | La Spaghetteria Ristorante | 132 Lygon St, Carlton

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Friday 12th July 2019

9:00 Plenary 4 | Heinrich Lang | From: Small Tailor-made Molecules To: New

Materials

Chair: Paul Donnelly

Session Chair: Curtis Ho

9:50 Masnun Naher | Metal Complexes for Molecular Electronics: Explorations of

Thioether Anchor Groups

10:10 Sigrídur Suman | Ligand Exchange Reaction and Catalysis of the Conversion

of Cyanide and Thiosulfate to Thiocyanate and Sulfite by a Molybdenum

Complex

10:30 Morning Tea

Session Chair: Jamie Hicks

11:00 Nicholas Tan | Rhodium (I)-Vinyl Complexes as Effective Initiators in the

Stereospecific Polymerization of Phenylacetylene

11:20 William Erb | An unprecedented diversity of 1,3-disubstituted ferrocenes through

the halogen ‘dance’ reaction

11:40 Zhifang Guo | Direct reaction—a simple route to synthesis

organoioamidodidolanthanoid(II/III) complexes

17:30 Special Topic 2 | Mark Rizzacasa | Married at First Sight: Total Synthesis and

Metal Complexes

Chair: Richard O’Hair

12:30 BBQ and Drinks

Poster Presentations

P1 Weam Altalhi | A Mechanistic Study of Ruthenium (II) Catalysed C-H Amidation and

Thioamidition

P2 Stephen Best | Charting the Reaction Coordinate in ‘Beryllocene’

P3 Lian Burt | Alkynyltellurolate Ligands and a Solvatochromic Rhenium(I) Complex

P4 Chiara Caporale | Single-Molecule Magnets: Lanthanide - β Diketonates “Triangles”

P5 Glen Deacon | Use of Ag(C6F5) or Bi(C6F5)3 instead of HgAr2 reagents in redox

transmetallation/protolysis reactions of free lanthanoid metals

P6 Deepamali Dissanayake | Lewis acids: Versatile catalysts for fundamental

transformations and polymerisations

P7 Jun Du | Optical Nonlinearities of Y-shaped and H-shaped Arylalkynylruthenium

Complexes

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P8 James Findlay | A [3]Rotaxane With Coupled Rotary and Linear Shuttling Motion

P9 Palak Garg | Bimetallic Group 14 Complexes Stabilised by Bis(N,N’-diarylamidinate)

Ligand

P10 Chuanzhu Gao | Antitumor dinuclear platinum (II) complexes with DNA imbedding

groups

P11 Michael Hall | Synthesis and Reactivity of Carbon-Rich and Cumulenylidene Ligands

in Iron and Ruthenium Complexes

P12 Daniel Harrison | Simple Metalation of Terminal Acetylenes: Synthesis of High Purity

Metal Acetylide Half- Sandwich Complexes

P13 Megan Herdman | Bismuth(III) phosphinate 1D-coordination polymers as

antibacterial additives

P14 Curtis Ho | Applications of Gold Cocatalysis & New Phosphine Ligands for Palladium-

Catalysed Cross-Couplings

P15 Ryan Huo | Confirmation of Redox Transmetallation/Protolysis Reaction Between

HgC6F5, lanthanoid metals and protic agents

P16 Dafydd Jones | Synthesis of New, Super Bulky β-Diketiminate Ligands and their

Application in Low-Oxidation State Metal Chemistry

P17 Marcus Korb | Diferrocenyl Co- and Fe-Carbonyl Clusters

P18 George Laffan | Synthesis and Spectroelectrochemical Studies of Ruthenium Alkynyl

Complexes

P19 Richard Manzano | The odd nature of tungsten C3 and C5 complexes

P20 Aidan McKay | Towards the Assembly Triple Hydrogen Bonded Transition Metal

Complexes

P21 Mahbod Morshedi | A Dipolar Molecular Switch for Nonlinear Optics

P22 Shazia Nawaz | Synthesis and characterization of bismuth (III) phosphonates as

antimicrobial polymeric materials

P23 Asif Noor | A one-pot route to thioamides and Amidines discovered by fundamental

gas-phase studies

P24 Richard O’Hair | A New Approach to Design MOF Based Catalysts

P25 Chee Onn | Selenium functionalised metal-carbon chains –

Alkynylselenolatoalkylidynes (LnMC–Se–CCR)

P26 Parvin Safari | Electron transfer processes and mixed-valence chemistry: studies with

metal complexes featuring carbon-rich ligands

P27 Lachlan Sharp-Bucknall | Reactivity of Newly Discovered Trans-Difluorogold(III)

Complexes

P28 Cory Smith | Experimental and Theoretical Properties of Low-Oxidation State

Aluminium Amidinate Complexes

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P29 Nigel Lucas | Superphenylphosphines: Nanographene-based Ligands that Direct

Coordination and Bulk Assembly

P30 Rachel Steen | Selective Activation of Alkynes through Cumulene Intermediates

P31 Lian Stephens | Synthesis of Novel Bismuth Tetrazole Thiolate Complexes as

Potential Antimicrobials

P32 Sigridur Suman | Biological Studies of a Molybdenum based Cyanide Poisoning

Antidote

P33 Yu Qing Tan | A new rotational isomer of bis(pentafluorophenyl)mercury [Hg(C6F5)2]

P34 Quinn van Hilst | Synthesis, Characterization and Biological Activity of Select [Pt(2-

pyridyl-1,2,3-triazole)2]2+ “Click” Complexes

P35 Daniel Van Zeil | Catalytic activity of N-heterocyclic carbene Ag(I) amides

P36 Koushik Venkatesan | Deep Blue Organic Light Emitting Diodes Based on N-

Heterocyclic Carbene Platinum(II) Complexes

P37 Huan Wang | Synthesis, Linear Optical, and Second-/Third-Order NLO Properties of

Porphyrin-Bridged Push-Pull Ruthenium Complexes

P38 Zilin Wang | Desulfination versus decarboxylation as a means of generating three-

and five- coordinate organopalladium complexes [(phen)nPd(C6H5)]+ (n = 1 and 2) to

study their fundamental bimolecular reactivity

P39 Steven Welsh | Early transition metal poly(methimazolyl)borate complexes

P40 Yang Yang | A novel transition-metal assisted approach to amide synthesis directed

by mechanistic studies

P41 Kuppusamy Yuvaraj | Reductive Trimerization of CO to the Deltate Dianion using

Activated Magnesium(I) Compounds

P42 Ling Zhang | Towards High-Generation Ruthenium Alkynyl Dendrimers for Nonlinear

Optics

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The Organising Committee gratefully acknowledges the support of our

sponsors:

Plenary Lectures

12 12th Australasian Organometallics Meeting

The chemistry of boron with pyrrole ligands: tales from the

world of porphyrins, corroles, phthalocyanines and

BODIPY

Penelope J. Brothers

Research School of Chemistry, Australian National University

Over recent years we have investigated the chemistry of boron with pyrrole-containing

ligands, of which the best known are porphyrins. Boron porphyrins are unique in

containing two boron atoms per porphyrin ligand. Highlights of this chemistry have

been the development of a diboryl porphyrin and a diboranyl porphyrin containing a

B-B bond which forms through spontaneous reductive coupling of the diboryl. More

recent work extends the coordination of boron to further ligands in the tetrapyrrole

family, notably corrole, phthalocyanine, porphyrazine and calixphyrin. Although these

ligands are closely related, we observe some significant differences in the boron

chemistry, including stereochemistry and chemical reactivity. As an example, we have

isolated boron hydride corrole complexes, including an unusual example of a complex

containing a B-H-B group coordinated to the cavity in the corrole. Finally, the well-

known BODIPY fluorophore is a boron dipyrrole complex, and using our expertise on

the chemistry of boron we have been prepared BODIPY-carbohydrate conjugates

which may have application ion sugar sensing and carbohydrate structure and

function.

B2OF2(porphyrin) B2OF2(corrole)

B2HPh2(corrole)

Plenary Lectures


My 40-year organometallic journey through the Periodic

Table with frequent stops at the rare-earth elements

Frank T. Edelmann

Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, Germany

This lecture is intended to provide an overview of the various aspects of our

organometallic chemistry studied at different universities (Hamburg, Edmonton,

Honolulu, Calgary, Göttingen and Magdeburg) during the past four decades. Early

highlights include e.g. the synthesis of CpCoS2N2, the first diaryl lead compound,

Pb[C6H2(CF3)3-2,4,6]2, and the dimerization of a phosphaalkyne by reaction with

decamethylsamarocene. Publications from Göttingen during the late 80's and early

90's on f-element amidinates made very clear the broad scope for new and possibly

useful chemistry offered by amidinate and related diazaallylic ligands. More recent

exploration of metallasilsesquioxanes and various sandwich complexes (including

triple- and tetra-decker sandwich complexes) of lanthanides and actinides will also be

described.

Word cloud illustrating our main research interests

Plenary Lectures


Synergistic Cooperation between Mechanistic

Investigations and Catalysis: Towards Rational Design

Mónica H. Pérez-Temprano*

Institute of Chemical Research of Catalonia (ICIQ)

The sustainable synthesis of relevant organic scaffolds for their use in the

pharmaceutical, agrochemical and material sectors constitutes one of the most urgent

challenges that the chemical community needs to overcome. Our ideal approach for

tackle this problem is the rational design and development of catalytic processes

based on fundamental mechanistic understanding. Surprisingly, this strategy remains

a largely unresolved challenge for academic and industrial chemists.

This work will describe our recent efforts not only to provide critical mechanistic

information on well-known reactivity, but also to understand, discover, design and

develop more efficient transition metal-catalyzed reactions by trapping and/or

synthesizing key reaction intermediates and using them as “knowledge building

blocks” for rational design (Figure 1).[1]

Figure 1. Our approach: trapping reaction intermediates for rational design.

References

[1] (a) J. Sanjosé-Orduna, D. Gallego, A. Garcia-Roca, E. Martin, J. Benet-Buchholz, M. H. Pérez-

Temprano, Angew. Chem. Int. Ed. 2017, 56, 12137. (b) J. Sanjosé-Orduna, J. M. Sarria Toro, M. H.

Pérez-Temprano, Angew. Chem. Int. Ed. 2018, 57, 11369.

[TM]

[TM]

[TM] ✓ improving the efficiency of

well-established transformation

✓ exploring innovativereactivity patterns

Trapping Reaction Intermediates as

“Knowledge Building Blocks”

Plenary Lectures


From: Small Tailor-made Molecules

To: New Materials

Heinrich Lang

Technische Universität Chemnitz, Faculty of Natural Sciences, Inorganic Chemistry

Within this presentation a brief overview of our group’s topics in the field of Material

Sciences will be given.

One focus of the talk will be directed to the use of organometallic and metal-organic

compounds based on different transition metals (for example, Cu, Ru and Co) as

precursor molecules in gas-phase (Chemical Vapour Deposition, Atomic Layer

Deposition) and spray-coating deposition technologies for the generation of thin,

dense and conformal metal films and patterns.

Also the use of combustion-CVD and especially 2D-inkjet printing of metal-organic

inks to produce conductive and semi-conductive layers on flexible substrates will be

discussed.

A straightforward synthetic methodology for the generation and stabilization of

conductive and magnetic metal as well as metal oxide nanoparticles by using single-

source complexes, including LnM(O2CCH2(OCH2CH2)2OMe)m (LnM = Ag, Cu(PR3)2,

Au(PR3), Ru(PR3)2(CO)2, Pd(PR3)2, Pt(PR3)2, Rh, Mn, Co, Ni, Fe, …; m = 1, 2, 3) as

precursors will be envisaged.

Finally, the possibility to apply metal nanoparticles for joining materials at low

temperature using the soldering process will be reported, as well as laser ablation for

the generation of metallic structures from metal-organic complexes.

Keynote Lectures


Bismuth Nanocellulose Composites and their Efficacy

Towards Multi-Drug Resistant Bacteria

Melissa V. Werrett,1 Megan E. Herdman,1 Liam J. Stephens,1 Rajini Brammananth2

Warren Batchelor,3 Maisha Maliha3 and Phil C. Andrews1*

School of Chemistry,1 Department of Microbiology2 and BioPRIA: Department of Chemical Engineering,3 Monash University.

Antimicrobial resistance is causing an alarming number of deaths in hospitals and

healthcare facilities. Medical devices (eg: bandages, implants) are high risk areas

regarding infection. Silver and its compounds are often used as additives in

antibacterial materials since they display broad spectrum activity, at relatively low

loadings.1 However, the predominance of silver in a range of broad-spectrum

antimicrobial products has generated significant concerns surrounding toxicity,

environmental accumulation and acquired bacterial resistance.2 Consequently, there

is a crucial need to find new, safe alternatives to silver-based antimicrobial additives.

A series of poorly soluble phenyl bis-phosphinato bismuth(III) complexes

[BiPh(OP(=O)R1R2)2] have been synthesised and characterised, and shown to have

effective antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus

(S. aureus), methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-

resistant Enterococcus (VRE).3

The bismuth complexes were incorporated into microfibrillated (nano-) cellulose

generating a bismuth-cellulose composite, as paper sheets or hydrogels. Antibacterial

evaluation indicates that the Bi-cellulose materials have analogous or greater activity

against Gram positive bacteria when compared with commercial silver-based

additives (Figure 1).

Figure 1: (Left) Backscattered electron

image of the Bi-nanoceullose

composite. (Right) Zone of inhibition

assay against VRE, using the Bi-

nanoceullose composite. Bismuth

complex loaded at 0, 0.1, 0.5, 1 and 5

wt%. Ag: silver sulfadiazine at 0.5 wt%.

References

[1] K. Mijnendonckx, N. Leys, J. Mahillon, S. Silver and R. Van Houdt, BioMetals, 2013, 26, 609–621.

[2] J.Y. Maillard and P. Hartemann, Crit. Rev. Microbiol., 2013, 39, 373–383.

[3] M. V. Werrett, M. E. Herdman, R. Brammananth, U. Garusinghe, W. Batchelor, P. K. Crellin, R. L. Coppel and P. C. Andrews, Chem. Eur. J., 2018, 24, 12938–12949.

Keynote Lectures


A tale of two cities: Electrostatic potentials are a chemists

best friend and new beginnings with trigonal lanthanoid

magnets

Rebecca O. Fuller

School of Molecular and Life Science, Curtin University, Bentley, WA

Organometallic chemistry and magnetism have always seem to be a part of the

chemist I am. Primarily during my PhD, organometallic molecules were used as

precursors for the synthesis of magnetic particles. It was only later during my

postdoctoral studies I was introduced to the wonderful world of group 8

cyclopentadienyl dicarbonyl metal halides [CpxM(CO)2X].[1] I learnt how electrostatic

potentials and Hirshfeld surfaces can be used to generate a wealth of knowledge

about these fascinating molecules. I will share with you a little of this story and how

distant interactions rather than close van der Waals contacts played a significant role

in the crystallisation of cyclopentadienyl ruthenium bromide with hexabromoethane.[2]

After recently commencing a DECRA at Curtin University my research focus has

shifted to the development of new magnetic molecules based on pyridyl-

betadiketonates and verdazyl ligands. To date trinuclear lanthanoid systems for the

investigation of toroidal spin arrangements have been prepared. We have also made

significant steps towards the synthesis of a radical ligand to be use to form complexes

with an organolanthanide species.

(left) Hirshfeld surface use to depict close contacts. (right) Trinuclear TbIII complex.

References

[1] R. O. Fuller, C. S. Griffith, G. A. Koutsantonis et al. CrystEngComm, 2012, 14, 812.

[2] R. O. Fuller, C. S. Griffith, G. A. Koutsantonis et al. CrystEngComm, 2012, 14, 804.

Keynote Lectures


High-Field Pulse EPR: A New Biophysical Toolbox for the Study of

Metalloenzymes

Nick Cox

Research School of Chemistry, Australian National University, Acton ACT, Australia

High-field Pulse Electron Paramagnetic Resonance (EPR) has recently emerged as a

powerful technique in the study of biological systems [1]. It represents a sensitive, non-

invasive, site-selective spectroscopy for the analysis of both molecular and

macroscopic properties. With the support of the ARC and the Max Planck Institute for

Chemical Energy Conversion in Mülheim, we are establishing Australia’s first high-

field (3 T, W-band) pulse EPR facility unique to the Asia-Pacific region and designed

to serve EPR spectroscopists across Australia. EPR at higher magnetic fields

enhances sensitivity [1], extends the range of systems amenable for study, and allows

implementation of new cutting-edge multidimensional pulse EPR methods [2].

In this talk I will describe results on nature’s water splitting catalyst, a pentaoxygen

tetramaganese calcium (Mn4O5Ca) cofactor that is found in a unique pigment–protein

complex known as Photosystem II. Structural evolution of the cofactor through its

catalytic (S-state) cycle can be correlated with its magnetic spin state. In “inactive” S-

states the cofactor adopts a low ground spin state whereas in the “active” S-states it

instead adopts a high spin ground state [3]. Intermediates which facilitate cofactor

activation can be isolated and characterized. It is this structural flexibility that allows

redox tuning of the cofactor and provides a means via which the substrate water

access to the cofactor is regulated [4].

References

[1] Cox N, Nalepa A, Pandelia ME, Lubitz W, Savitsky A. Methods in enzymology 563, 211-249 (2015)

[2] Cox N, Retegan M, Neese F, Pantazis DA, Boussac A, Lubitz W. Science 345, 804-808 (2014)

[3] Krewald V, Retegan M, Neese F, Lubitz W, Pantazis DA, Cox N. (2016) Inorg. Chem. 55, 488-501

[4] Perez-Navarro M, Neese F, Lubitz W, Pantazis DA, Cox N. (2016). Curr. Opin. Chem. Biol. 31, 113-119.

Keynote Lectures


Main Group Pyridyl Ligands: From the Molecular to the

Supramolecular

Annie L. Colebatch,*,a,b Eric S. Yang,a Alex J. Plajer,a Álvaro García-Romero,c

Andrew D. Bond,a Raúl García-Rodríguez,c and Dominic S. Wrighta

a Department of Chemistry, University of Cambridge, United Kingdom

b Research School of Chemistry, Australian National University, Australia

c Facultad de Ciencias, Universidad de Valladolid, Spain

Pyridyl groups are one of the most widely encountered donor moieties in inorganic

chemistry thanks to their versatility, robustness and tunable nature, finding application

in catalysis, photochemistry, supramolecular and bioinorganic chemistry. Despite their

widespread use, amongst the thousands of pyridyl-derived ligands that are known,

examples featuring main group elements are severely under-represented. We have

incorporated main group elements in tris(pyridyl) ligands, and found that this provides

a new handle by which to modulate ligand properties.[1-3] This offers opportunities to

synthesise stable supporting ligands[2] or incorporate reactive main group sites to take

advantage of their Lewis acidic[1] or Lewis basic[3] nature. Recent work has extended

these molecular ligand design approaches to the preparation of supramolecular

architectures, providing a route to mixed-metal systems.

Figure 1. Examples of molecular and supramolecular structures featuring main group pyridyl ligands.

References

[1] A. J. Plajer, A. L. Colebatch, F. J. Rizzuto, P. Pröhm, A. D. Bond, R. García-Rodríguez, D. S. Wright

Angew. Chem. Int. Ed. 2018, 57, 6648 – 6652.

[2] A. J. Plajer, A. L. Colebatch, M. Enders, Á. García-Romero, A. D. Bond, R. García-Rodríguez, D. S.

Wright Dalton Trans. 2018, 47, 7036 – 7043.

[3] S. Hanf, R. García-Rodríguez, S. Feldmann, A. D. Bond, E. Hey-Hawkins, D. S. Wright Dalton Trans.

2017, 46, 814 – 824.

Special Topics


Nineteenth Century Organometallics in Melbourne

Ian D. Rae

Honorary Professorial Fellow, School of Chemistry, University of Melbourne

Australian organometallic chemistry did not begin in Sydney in the 1920s, but at the

University of Melbourne in the late 1880s. Norman Wilsmore, working under the

direction of Professor Masson, made repeated attempts to prepare diethyl

magnesium. These included transmetallation reactions, for which Wilsmore had to

prepare diethyl zinc and diethyl mercury. Extensive discussion of their failures, and

their conclusion that magnesium does not form alkyl derivatives, were reported to the

Chemical Society (London) and the 1891 meeting of the Australasian Association for

the Advancement of Science in Christchurch, New Zealand.

Special Topics


Married at First Sight:

Total Synthesis and Metal Complexes

Mark A. Rizzacasa,* Liselle Atkin, Bill Zongjia Chen, Paul Donnelly, Alex Rafaniello,

Michael Ricca, Angus Robertson and Jonathan M. White

School of Chemistry, The Bio 21 Molecular Science and Biotechnology Institute,

University of Melbourne, Parkville, Victoria, 3010

The total synthesis of natural products is a cornerstone of organic chemistry driving

the development of new reactions and reagents. In addition, total synthesis can be

utilized to confirm structure and provide quantities of rare natural products for further

biological evaluation. Metal mediated reactions, in particular, are often critical in

complex molecule synthesis and some recent targets within the group such as the

citrafungins (revised structures) and the spirodienals have important transformations

that rely on transition metal complexes. This work has led to a new program focused

on the synthesis and application of Mn and Co complexes for the regioselective

hydration of polar alkenes. This presentation will detail our latest results in this area.

OO

(CH2)7CH3

O

HO2C

HO2C

HO2C

O

H

HO

HO2C

HCitrafungin A

(revised structure)

O

OMe

OH

MeO

Me Me

OH

Me

Me

Me

OH

Me Me

CHO

Spirodienal C

Mn Cat., PhSiH3

O2, iPrOH

O OTBDPSOO OTBDPSO

OH80%

MnIII(EtOSALPN)acac

Oral Presentations


A Mechanistically Guided Approach to C-H Bond

Amidation

Alasdair I. McKay,a Weam A. O. Altalhi,a Paul S. Donnelly,a Allan J. Canty,b Richard

A. J. O’Hair*a

a School of Chemistry, University of Melbourne

b School of Physical Sciences, University of Tasmania,

Transition-metal catalysed C-H bond functionalization reactions have emerged as

atom efficient strategies for chemical synthesis by avoiding tedious substrate

preactivation steps and eliminating waste. Whilst C-H arylation and C-H alkyne

insertion reactions have been extensively investigated,[1] related C-H amidation

procedures have received considerably less attention.[2] Amides are a very important

function group widely applied in industry and drug design. Transition metal catalysed

methods to prepare amides have principally employed expensive and precious

rhodium based precatalysts, which are environmentally disadvantageous, especially

for future industrial applications.[3]

In this contribution we develop inexpensive C-H amidation catalysts. We characterise

key intermediates using electrospray ionisation mass spectrometry (ESI-MS). Which

combined with DFT calculations enables a detailed examination of the mechanism of

transition metal catalysed C-H bond amidation.

Figure 1. Metal catalysed insertion of an iso(thio)cyanate into a C-H bond.

References

[1] D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev. 2010, 110, 624-655.

[2] K. D. Hesp, R. G. Bergman and J. A. Ellman, J. Am. Chem. Soc., 2011, 133, 11430-11433.

[3] Y. Park, K. T. Park, J. G. Kim, S. Chang, J. Am. Chem. Soc. 2015, 137, 4534-4542.

Oral Presentations


In-depth study of a Highly Efficient Enantioselective

Intramolecular Hydroamination Reaction

Daven J. Foster, Pengchao Gao, Gellért V. Sipos, Reto Dorta*

School of Molecular Sciences, University of Western Australia

Following the introduction of chiral, cationic NHC-iridium complexes as catalysts for

the intramolecular hydroamination reaction of unactivated alkenes,[1] work has been

put into optimising conditions and obtaining cyclised products beyond the basic

methylated pyrrolidine motif. These new systems require lower catalyst loadings and

milder reaction conditions to produce high yields and optical purities of the cyclised

products, therefore significantly expanding the scope compared to earlier rare-earth

metal and ETM systems.[2] A comparison of catalysts and mechanistic investigations

into the reaction pathway will also be discussed.

Figure 1: Asymmetric iridium catalysed hydroamination reaction involving cyclisation of a variety of

amino olefin substrates

References

[1] a) Sipos, G., Ou, A., Skelton, B.W., Falivene, L., Cavallo, L. and Dorta, R. Chem.: Eur. J.,

2016, 22(20), 6939-6946. b) Gao, P., Sipos, G., Foster, D. and Dorta, R. ACS Catalysis, 2017, 7(9),

6060-6064.

[2] For selected references: a) Wood, M. C.; Leitch, D. C.; Yeung, C. S.; Kozak, J. A.; Schafer, L. L.

Angew. Chem. Int. Ed. 2007, 46, 354. b) Zhang, X.; Emge, T. J.; Hultzsch, K. C. Angew. Chem. Int. Ed.

2012, 51, 394. c) Manna, K.; Eedugurala, N.; Sadow, A. D. J. Am. Chem. Soc. 2015, 137, 425.

Oral Presentations


Theoretical insights into ligand photorelease mechanisms:

new types of 3MC states

Isabelle M. Dixon,a* Adrien Soupart,a Fabienne Alary,a Jean-Louis Heully,a Sylvestre

Bonnet,b Paul I. P. Elliottc

aLaboratoire de Chimie et Physique Quantiques, CNRS/U. Toulouse, France bLeiden Institute of Chemistry, Leiden U., The Netherlands

cDepartment of Chemistry and Center for Functional Materials, U. Huddersfield, UK

The efficiency and selectivity of photoinduced ligand release is key to applications

such as photoactivated chemotherapy (PACT)[1] or light-triggered molecular

machines.[2] Microscopic mechanisms by which this process can be controlled still

require considerable attention and fundamental studies. Bonnet’s group has recently

reported the controlled photorelease of monodentate thioether ligands from Ru(II)

prodrugs.[3] On the other hand, Elliott’s group is interested in the controlled

photorelease of bidentate ligands.[4] In joint experimental-theoretical studies, using a

combination of DFT-based methods, we have shown that the topology of the lowest

triplet excited potential energy surface (3PES) was crucial in the ligand photorelease

efficiency. Different types of original 3MC excited states of peculiar geometries were

proposed to be key to the photorelease mechanisms,[5,6,7] and will be presented here.

References

[1] Gasser et al. Chem. Sci. 2015, 5, 2660. Turro et al. Coord. Chem. Rev. 2015, 282-283, 110.

[2] Credi et al. Eur. J. Inorg. Chem. 2018, 4589 and references therein.

[3] Bonnet et al. Inorg. Chem. 2013, 52, 9456.

[4] Elliott et al. Angew. Chem. Int. Ed. 2013, 52, 10826.

[5] Alary, Bonnet et al. Inorg. Chem. 2016, 55, 4448.

[6] Dixon, Elliott et al. Phys. Chem. Chem. Phys. 2017, 19, 27765.

[7] Dixon, Elliott et al. Inorg. Chem. 2018, 57, 3192.

Oral Presentations


Detection and Reactivity of a Bridging C1 Ligand

Harrison J. Barnett, Anthony F. Hill*

ANU Research School of Chemistry. Australian National University, Sullivans Creek

Road, Acton, ACT, 2601

Monoatomic carbon bridges (-carbido) are notably rare in transition metal chemistry.

When considering μ-carbido complexes, two formal bonding modes are reported; the

symmetric cumulenic (M=C=M), and the asymmetric metallacarbyne (M≡C-M). The

cumulenic bonding mode is scarce in the literature by comparison due to limited

synthetic routes and metal centre electronic requirements.

This work follows on from the synthesis of a simple rhodium cumulenic -carbido

species, [Rh2(-C)Cl2(PPh3)4], which was formed via activation of a thiocarbonyl ligand

with catecholborane.[1] The labile phosphines can be removed under mild conditions

and replaced with bridging bidentate ligands, forming “A-frame” carbido complexes,

such as [Rh2(-C)Cl2(-dppm)2].

Initial reactivity studies of the cumulenic -carbido ligand have provided inter alia the

first structural examples of 2-halocarbyne species with both chlorine and bromine.[2]

Simplified molecular structures of [Rh2(-C)Cl2(-dppm)2] and [Rh2(-C)(-Br)(-CBr)Br4(-dppm)2]

References

[1] H. J. Barnett, L. K. Burt and A. F. Hill, Dalton Trans., 2018, 47, 9570

[2] H. J. Barnett, A. F. Hill, Chem. Commun., 2019, 55, 1734

Oral Presentations


Synthesis and Properties of 2,7-alkynyldihydropyrene

Photochromic Switches

Angus A. Gillespie, Max Roemer, George A. Koutsantonis*

School of Molecular Sciences, The University of Western Australia

The manipulation of single molecules to mimic the properties of electronic circuit

components is the cornerstone of molecular electronics. The dihydropyrene (DHP)

family is a promising example of photochromic switches that under the irradiation of

visible light isomerise to the cyclophanediene (CPD) form that can return to the DHP

form via UV irradiation or heat. The implementation of DHP in molecular circuits

requires a mode of contact between the bridge and electrode, surface contacting

groups.1

Investigation into the conductive properties of DHPs has been limited to functional

substitutions at the 4/5 and 9/10 positions. This presentation will describe the

synthesis of DHPs with alkynyl substituents at the 2/7 positions and their electronic

and photochromic properties (Figure 1). Further functionalisation of these compounds

can promote an alternative conductance pathway and new electronic and

photochromic behaviours can be observed.

Figure 1: Photochromic isomerisation between the DHP (closed) and CPD (open) forms. R = Ethyl,

Butyl

References

[1] Roldan, D.; Kaliginedi, V.; Cobo, S.; Kolivoska, V.; Bucher, C.; Hong, W.; Royal, G.; Wandlowski, T., Charge transport in photoswitchable dimethyldihydropyrene-type single-molecule junctions. J. Am. Chem. Soc. 2013, 135 (16), 5974-7.

TIPS

TIPS

RR

TIPS

TIPS

RRvis.hv

UVhvD

Oral Presentations


Accessing unsupported magnesium 2-aza allyl complexes

Jamie A. Greer, Victoria L. Blair, Phil C. Andrews*

School of Chemistry, Monash University

2-aza allyl amides are a class of organometallic complexes predominantly applied in

[2+3] cycloaddition reactions. They are generally synthesised via deprotonation of

benzylphenylmethanimine derivatives via strong group 1 bases. These compounds

have seen an increase in interest recently due to demonstrations of their capability to

cross couple with aryl halides without the need for heavy metals.[1] Furthermore,

accompanying pyridyl R-groups have been used to form stable complexes using less

electropositive metals, such as aluminium, that are capable of undergoing [3+3]

dimerisation reactions when irradiated with UV light.[2]

Previous research by the Andrews groups have structurally characterised several Na

and K analogues of these systems that can be synthesised through direct

deprotonation, or via a beta-hydride elimination route from dibenzylamine derivatives.

The use of these heavier alkali metal complexes has allowed for favourable

transmetalation with magnesium salts, a feat generally unachievable via alternative

routes, which has been conducted in order to gauge their comparative reactivity. We

will report on some of the [3+3] cyclisation dimerisation observed from these

experiments as well as the unexpected radical behaviour of these species.

Figure 1: Solid state monomer of {[PhC(=CH2)NCH2Ph]2Mg·THF2}

References

[1] M. Li, S. Berritt, L. Matuszewski, G. Deng, A. Pascual-Escudero, G. B. Panetti, M. Poznik, X. Yang,

J. J. Chruma and P. J. Walsh, J. Am. Chem. Soc., 2017, 139, 16327-16333.

[2] S. Suárez-Pantiga, K. Colas, M. J. Johansson and A. Mendoza, Angew. Chem. Int. Ed., 2015, 54,

14094-14098.

Oral Presentations


Switchable Heterometallic Supramolecular Cages

Lynn S. Lisboa, James D. Crowley*

Department of Chemistry, University of Otago

Homodimetallic supramolecular cages, architectures composed of two metal centres

bridged by connecting ligands, have a central cavity that can host guest molecules.1

The cages’ affinity to bind guest molecules can be exploited as potential drug delivery2

and catalytic3 systems. However, a major limitation of supramolecular cages is its

inability to release its guest molecule without complete or irreversible disassembly

upon activation.1b, 4

We aim to synthesise platinum(II)/palladium(II) heterometallic cages capable of guest

release through partial disassembly/reassembly via the addition/elimination of an

external stimulus. We will do so by exploiting the difference in lability between platinum

and palladium.

Figure 1: Proposed assembly and stimulated partial disassembly of a heterometallic PtII/PdII cage.

References

[1] (a) Cook, T. R.; Stang,P. J. Chem. Rev. 2015, 115 (15), 7001-7045; (b) McConnell, A. J.; Wood, C.

S.; Neelakandan, P. P.; Nitschke, J R. Chem. Rev. 2015, 115 (15), 7729-7793.

[2] Zheng, Y. R.; Suntharalingam, K.; Johnstone, T. C .; Lippard, S. J. Chem. Sci. 2015, 6 (2), 1189-

1193.

[3] (a) Martí-Centelles, V.; Lawrence, A. L.; Lusby, P. J. J. Am. Chem. Soc. 2018, 140 (8), 2862-2868;

(b) Ueda, Y.; Ito, H.; Fujita, D.; Fujita,M. J. Am. Chem. Soc. 2017, 139 (17), 6090-6093.

[4] Kim, T. Y.; Vasdev, R. A. S.; Preston, D.; Crowley, J. D. Chem. Eur. J. 2018, 24 (56), 14878-14890.

Oral Presentations


Beryllium

Albert Paparo, Cameron Jones*


Fear of death and injury is a blessing and at the same time a great obstacle for

chemists. While keeping us alive, it also limits the resources invested into research on

explosive, radioactive, highly toxic or otherwise dangerous materials. Beryllium is

considered to be one of the most toxic elements, hence its chemistry has been left

mostly unexploited.[1] Curiosity has trumped our drive for self-preservation, and we are

exploring the basic chemistry of reactive beryllium species.

The reason for our interest is that there are now numerous examples of low-valent

main-group metal compounds that are capable of activating environmentally relevant

small molecules such as CO2 in a transition-metal-like fashion.[2] The s block is

represented by the Mg–Mg bonded dimers and their rich reactivity with small

molecules.[3] However, low-valent Be or Ca complexes are confined to single

examples.[4] Here, we reveal the very first Al–Be bonded species. A collection of

curiosities generated along the track will be also presented (see Scheme 1).

Scheme 1. Al–Be species and other curiosities.

References

[1] D. Naglav, M. R. Buchner, G. Bendt, F. Kraus, S. Schulz, Angew. Chem. Int. Ed. 2016, 55, 10562-

10576.

[2] a) P. P. Power, Chem. Rev. 1999, 99, 3463-3504; b) P. P. Power, Nature 2010, 463, 171-177; c) T.

Chu, G. I. Nikonov, Chem. Rev. 2018, 118, 3608-3680.

[3] a) S. P. Green, C. Jones, A. Stasch, Science 2007, 318, 1754-1757; b) C. Jones, Nat. Rev. Chem.

2017, 1, 0059.

[4] Be(0): a) M. Arrowsmith, H. Braunschweig, M. Celik, T. Dellermann, R. D. Dewhurst, W. C. Ewing,

K. Hammond, T. Kramer, I. Krummenacher, J. Mies, K. Radacki, J. K. Schuster, Nat. Chem. 2016,

8, 890–894; b) G. Wang, L. Freeman, D. Dickie, R. Mokrai, Z. Benkő, R. Gilliard, Chem. Eur. J.

2019, 25, 4335-4339. Ca(I): S. Krieck, H. Gorls, L. Yu, M. Reiher, M. Westerhausen, J. Am. Chem.

Soc. 2009, 131, 2977-2985.

N

N

tButBu

Be Br

BeN

N

tBu

tBuBe

Br

N

NtBu

tBu

BeBr

Be

H

H

H

H

N

N

tBu

tBuBe

Br

H

H

H

H*

*

Li

NMe2

Me2N

CH3

Be

H3C

CH3

Li

NMe2

Me2NH3

CN

N

Dip

Dip

Al Be

Hal

Hal

N

N

Hal = Br, I

Dip = 2,6-iPr2C6H3

Oral Presentations


Porphyrins and Electron-Rich Alkynyl Complexes: A Step

toward Remarkable Redox-active Molecular Arrays for

Electronics or Photonics

Frédéric Paul

Univ Rennes, CNRS, ISCR, UMR 6226, F-35000 Rennes (France)

Tetra-arylporphyrins constitute appealing redox-active molecular platforms endowed

with interesting linear and nonlinear optical properties. When associated to electron-

rich alkynyl complexes, used as redox-switchable electron-releasing groups, the

resulting molecules can often present remarkable properties for developing molecular-

based devices for electronics or photonics.[1] Through several examples, we will

present our work in this field based on various families of derivatives always

associating simple porphyrin cores and various metal alkynyl complexes. Initially

focussed on the development of molecular wires such as 1+,[2] we will show how we

evolved toward the design of nonlinear electrochromes such as 2,[3] for instance,

before finally attempting to design redox-switchable luminophores such as 3 (Fig. 1),

the latter prospect turning out to be much more challenging than initially expected.

More interesting than the design and synthesis of these particular targets, we hope to

show that a proper understanding of the interplay between electron transfer and

photonic properties at the molecular level can lead to the design of new organometallic

molecules endowed with outstanding properties and tailored for addressing some of

the societal challenges of the future.

Fig 1. Some derivatives that will be discussed.

References

[1] (a) Marques-Gonzales, S.; Low, P. J. Aust. J. Chem. 2016, 69, 244. (b) Grelaud, G.; Cifuentes, M.

P.; Paul, F.; Humphrey, M. G. J. Organomet. Chem. 2014, 751, 181.

[2] Malvolti, F.; Le Maux, P.; Toupet, L.; Smith, M. E.; Man, W. Y.; Low, P. J.; Galardon, E.; Simonneaux,

G.; Paul, F. Inorg. Chem. 2010, 49, 9101.

[3] Merhi, A.; Grelaud, G.; Morshedi, M.; Abid, S.; Green, K. A.; Barlow, A.; Groizard, T.; Kahlal, S.;

Halet, J.-F.; Ngo, H. M.; Ledoux-Rak, I.; Cifuentes, M. P.; Humphrey, M. G.; Paul, F.; Paul-Roth, C. O.

Dalton Trans. 2018, 47, 11123.

Oral Presentations


Extending Alkali Metal Mediated Magnesiation from

nitrogen to phosphorus

Michael A. Stevens, Phil C. Andrews, Victoria L. Blair*


Metalation chemistry has been dominated by the alkyl lithiums and lithium secondary

amides.[1] In comparison to the wealth of knowledge on nitrogen based metalation

chemistry, there has been comparatively few studies on their heavier group 15

phosphorus analogues.[2,3] The electronic properties conferred on compounds by the

heavier elements can differ dramatically from the lighter ones.

Herein we report a comparative reactivity study of homologous nitrogen and

phosphorus based compounds with the sodium magnesiate complex

[(TMEDA)Na(TMP)2Mg(CH2SiMe3)]. These new bi-metallic bases are synergic

reagents combining the reactivity of an alkali metal with a less reactive metal, such as

magnesium or zinc. These bases have been found to react with unique

regioselectivity, as well as allowing mild reaction conditions. X-ray crystallography

structural studies, solution state NMR studies and electrophilic quenches studies will

be presented.

Scheme 1: The reaction of the sodium magnesiate base with P,P-diisopropylphenylphosphine, resulting

in the meta-magnesiated compound [(TMEDA)Na(TMP)(m-iPr2PC6H4)Mg(TMP)]

References

[1] R. E. Mulvey, Acc. Chem. Res. 2009, 42, 743–755.

[2] V. L. Blair, M. A. Stevens, C. D. Thompson, Chem. Commun. 2016, 52, 8111–8114.

[3] M. A. Stevens, F. H. Hashim, E. S. H. Gwee, E. I. Izgorodina, R. E. Mulvey, V. L. Blair, Chem. - A Eur. J. 2018, 24, 15669–15677.

Oral Presentations


Sodium-magnesiate facilitated cyclisation of imines via C-F

bond activation

Samantha A. Orr, T. Wollmann, Phil C. Andrews* and Victoria L. Blair*

School of Chemistry, Monash University, Clayton, Melbourne, Victoria, 3800

Imines are valuable building blocks for the synthesis of many complex molecules due

to their simple preparation. Applications of Schiff’s bases include ligands for metal-

complexation, preparation of amines and precursors for pharmaceutical scaffolds. Due

to their importance, efforts to develop new functionalisation methods are ongoing. A

concurrent interest we have is the synthetic design of fluorinated substrates, owing to

their medicinal relevance with a C-F bond appearing in 20% of new drugs.1 Transition

metals have generally dominated the field of C-F activation2 but more recently s-block

and low valent species have showed success.3

The work presented will focus on synthetic transformations of fluoro-substituted imines

employing our sodium-magnesiate bimetallic base and the monometallic counterparts.

Initial studies revealed a selective ortho-C-F activation of a pentafluoro-substituted aryl

imine, leading to the unprecedented cyclisation of two imine species (figure 1). The

resultant novel 8-membered carbon-nitrogen ring has been fully characterised by x-

ray crystallography and NMR spectroscopy, the scope has been extended and the

mechanistic pathway probed.

Figure 1: Reaction of pentafluoro-arylimine and sodium-magnesiate mediated C-F activation.

References

[1] K. Müller, C. Faeh, F. Diederich, Science, 2007, 317, 1881. [2] T. Fujita, K. Fuchibe, J. Ichikawa,

Angew. Chem. Int. Ed., 2019, 58, 390. [3] F. M. García-Valle, V. Tabernero, T. Cuenca, M. E. G.

Mosquera, J. Cano, Organometallics, 2019, 38, 894; C. Bakewell, A. J. P. White, M. R. Crimmin, J. Am.

Chem. Soc., 2016, 138, 12763.

Oral Presentations


Tris(styryl)isocyanurates: Towards New Dyes with Large Two-Photon Absorption Cross-Sections

Alphonsine NGO NDIMBA1,2, Amédée TRIADON1,2, Nicolas RICHY2, Mahbod

MORSHEDI1, Marie P. CIFUENTES1, Olivier MONGIN2, Frédéric PAUL2 and Mark

G. HUMPHREY1*

1Research School of Chemistry, Australian National University, Canberra, ACT 2601

(Australia)

2Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Université de

Rennes, Campus Beaulieu, 35042 Rennes Cedex (France)

Materials possessing third-order nonlinear optical properties have recently aroused

considerable interest due to potential applications in areas such as optical

limiting[1].1,3,5-Triaryltriazinanes-2,4,6-triones (1-X, more commonly known as

triphenylisocyanurates) have been reported by some of us as exhibiting remarkable

optical properties[2]. When Ru-alkynyl complexes ([Ru] = Ru(dppe)2) are appended in

place of the X substituents, the organometallic end groups enhance tremendously the

two-photon absorption cross-sections in compounds such as 1 compared to extended

all-organic 1-X analogues functionalized by electron-releasing X substituents (X =

NMe2) [2]. We were therefore curious to investigate the effect of this substitution in a

more conjugated tris(styryl) analogue. Accordingly, we will report herein the synthesis

of a family of tris(styryl)isocyanurates and our attempts to isolate the tris(styryl)

analogue of 1-X.

N

N

N

N

N

N

N

N

N

O

O OO

O O

O

O O

X X

X

X X

X

Ru

RuRuClCl

Cl1-X

12-X

Ru = RuPPh2Ph2P

PPh2Ph2P

References

[1] (a) G.S. He; L.-S. Tan; Q. Zheng; P.N. Prasad Chem. Rev. 2008, 108, 1245; (b) M. Pawlicki; H.A.

Collins; R.G. Denning; H.L. Anderson Angew. Chem. Int. Ed. 2009, 48, 3244 – 3266.

[2] G. Argouarch; R. Veillard; T. Roisnel; A. Amar; H. Meghezzi; A. Boucekkine; V. Hugues; O. Mongin;

M. Blanchard-Desce; F. Paul Chem. Eur. J. 2012, 18, 11811-11827.

Oral Presentations


Nucleophilic aluminium: Synthesis, structural and reaction

chemistry of the aluminyl anion

Jamie Hicks,a,b Jose M. Goicoecheab,* and Simon Aldridgeb,*

aResearch School of Chemistry, Australian National University, 2601

bChemistry Research Laboratory, 12 Mansfield Road, University of Oxford, OX1 3TA

Aluminium is the most abundant metal in the Earth’s crust and is widely exploited in a

number of key industrial processes. Being located in group 13 of the Periodic Table it

possesses four valence orbitals but only three valence electrons. Its reactivity is

therefore dominated by its electron deficiency and electropositivity: Al(III) compounds

are archetypal electrophiles. Last year, we reported that anionic Al(I) compounds can

act as nucleophiles, with the dimethylxanthene-stabilized potassium aluminyl

compound [K{(NON)Al}]2.[1] The complex has been shown to react in an

unprecedented ‘umpolung’ fashion as an aluminium-centred nucleophile in the

formation of a range of Al-E covalent bonds (E = H, C or metals), including in the

synthesis of the first nucleophilic gold compound [(NON)AlAuPtBu3].[2]

More recently, it has been found that by adding the potassium sequestering reagent

2.2.2-cryptand to the dimeric aluminyl complex, the first ‘naked’ aluminyl species of

the type [K(2.2.2-crypt)][(NON)Al] can be synthesised. This complex shows

remarkable reactivity towards aromatic molecules, for example inserting into the C-C

bond of benzene to give the 7-membered heterocycle [K(2.2.2-crypt)][(NON)AlC6H6]

(Figure 1).[3] This C-C bond activation of benzene was found to be reversible;

mechanistic details and functionalisation of the C-C bond activation will be discussed.

Figure 1. C-C bond activation of benzene by a monomeric aluminyl complex.

References

[1] J. Hicks, P. Vasko, J. M. Goicoechea, S. Aldridge, Nature, 2018, 557, 92–95.

[2] J. Hicks, Akseli Mansikkamäki, P. Vasko, J. M. Goicoechea, S. Aldridge, Nature Chemistry, 2019,

11, 237–241.

[3] J. Hicks, P. Vasko, J. M. Goicoechea, S. Aldridge, submitted.

Oral Presentations


New aluminium lanthanoid biphenolate complexes through

redox transmetallation protolysis

Angus C. G. Shephard,a Safaa H. Ali,a Glen B. Deacon,b Peter C. Junka

a College of Science and Engineering, James Cook University, Townsville Qld 4811,

Australia

b School of Chemistry, Monash University, Clayton Vic 3800, Australia

Carbon-bridged biphenol ligands have garnered significant attention in the field of

organometallic chemistry, particularly as lanthanoid biphenolate complexes. This

interest has stemmed from their ability to catalyse a range of organic transformations.

Access to these lanthanoid biphenolate complexes has typically been achieved via

ligand exchange reactions, involving treating the corresponding LnCpx, or

Ln{N(SiMe3)2}x with the desired biphenol ligand.1,2 An alternative, and much neglected,

synthesis of these complexes is afforded by redox transmetallation/protolysis (RTP)

(Scheme 1). These lanthanoid biphenolate complexes display further reactivity

towards metal alkyl reagents, forming both ionic, and non-ionic heterobimetallic

complexes. These new heterobimetallic complexes are expected to be active catalysts

for the ring opening polymerisation of rac-lactide. Herein, the synthesis and

characterisation of some heterobimetallic biphenolate complexes is described.

Scheme 1 – Synthesis of carbon-bridged biphenolate lanthanoid complexes by redox transmetallation protolysis, and subsequent metallation by trimethyl aluminium

References

(1) Deng, M.; Yao, Y.; Shen, Q.; Zhang, Y.; Sun, J. Dalt. Trans. 2004, 4, 944–950

(2) Qi, R.; Liu, B.; Xu, X.; Yang, Z.; Yao, Y.; Zhang, Y.; Shen, Q. Dalt. Trans. 2008, 7, 5016–5024

Oral Presentations


Synthesis of ruthenium diimine complexes for catalysis

Jeremy Stone1, Mark Spackman1, Paul Low1, George Koutsantonis1*

1 School of Molecular Sciences, The University of Western Australia

Converting small molecules such as CO2 and N2 to higher value products generally

requires the use of a transition metal catalyst. This work describes the synthesis of a

variety of organometallic complexes containing diimine ligands, which can be easily

modified to change the properties of the complex to be beneficial for such catalysis.

Starting from a versatile ruthenium naphthalene starting material (Fig. a) a range of

complexes can be reached with different steric, electronic and solubility properties.1

Examples include sterically hindered diimine ligands (Fig. b) and highly fluorous

ligands that could allow for homogeneous catalysis in supercritical CO2.2 The reactivity

of these complexes has been developed to show hydride and acetylide complexes

can be reached. Isolating hydride complexes is important for activating CO2 as it allows

for insertion into the metal hydride bond.3

a) b)

Figure a) General synthesis of ruthenium diimine complexes. Figure b) Crystal structure of sterically

hindered ruthenium diimine complex.

References

1. Stone, J.; Jago, D.; Sobolev, A.; Spackman, M.; Koutsantonis, G., Aust. J. Chem. 2018, 71 (4), 289-294.

2. Berven, B. M.; Koutsantonis, G. A.; Skelton, B. W.; Trengove, R. D.; White, A. H., Dalton Trans. 2011,

40 (16), 4167-4174.

3. Sordakis, K.; Tang, C.; Vogt, L. K.; Junge, H.; Dyson, P. J.; Beller, M.; Laurenczy, G., Chem. Rev. 2018,

118 (2), 372-433.

Oral Presentations


Exploring properties of novel Ga(III) and Bi(III) flavonolate

complexes

Kirralee J. Burke, Victoria L. Blair, Phil C. Andrews*


Flavonols (3-hydroxyflavones) are widely researched due to their ubiquitous presence

in dietary plants and their well-demonstrated in vitro anti-oxidant, anti-bacterial, and

anti-cancer properties.[1] While flavonols contain a facile O,O metal-chelating site

through the alpha-hydroxy ketone moiety, metal-flavonolate complexes remain

uncommon and examples are greatly limited to transition metals.[2]

Here we present the first examples of gallium(III) and bismuth(III) flavonolate

complexes. The in vitro biological activity of these compounds towards mammalian

and bacterial cells will be discussed. The luminescent properties of these novel

complexes will also be presented. Dimethylgallium flavonolate derivatives such as

[Ga(CH3)2(4DMAF)] (Figure 1) have been found to be highly emissive in both the solid

state and in solution, and their respective photophysical properties can be tuned by

altering the substituents on the flavonolate ligand.

Figure 1. Molecular structure of dimethylgallium(III) flavonolate complex [Ga(CH3)2(4DMAF)].

References

[1] A. Y. Chen, Y. C. Chen, Food Chem. 2013, 138, 2099.

[2] M. M Kasprzak, A. Erxleben, J. Ochocki, RSC Adv. 2015, 5, 45853.

Oral Presentations


Caught at Last! Isolation, Structural Characterization and

Gas-phase Studies of the [Ag10(H)8L6]2+ Nanocluster

Dication

Howard Z. Ma,* Alasdair I. McKay,* Jonathan M. White,* Roger J. Mulder,† A.

Mravak,‡ Michael Scholz,* Gavin E. Reid,* Evan J. Bieske,* Vlasta Bonačić-

Koutecký,‡ Richard A. J. O’Hair*

*School of Chemistry, University of Melbourne, Australia

†Biophysics Group, CSIRO Manufacturing, Australia

‡Interdisciplinary Center for Advanced Sciences and Technology, University of Split,

Croatia

Coinage metal nanoclusters (CMNs) continue to attract attention as models for

nanoparticles, for their structure and bonding arrangements, spectroscopic properties

and roles in catalysis. We have been using an approach that blends electrospray

ionization mass spectrometry (ESI-MS) to direct the bulk synthesis of CMNs, X-ray

crystallography, neutron diffraction and NMR spectroscopy for structural

characterization, and multistage mass spectrometry (MSn) experiments in conjunction

with Density Functional Theory (DFT) calculations to examine the chemistry of CMNs.

The [Ag10(H)8L’6]2+ cluster dication is observed to be a major ion in the ESI-MS

solutions containing a silver salt (AgBF4), the small bite angle bisphosphine ligand L’

= DPPM = bis(diphenylphosphino)methane and sodium borohydride (NaBH4). Like

the Scarlett Pimpernel, it has eluded capture for X-ray crystallographic

characterization. Our previous efforts at characterizing its structure employed VUV

photoionization in conjunction with DFT to predict a silver cluster core with a bicapped

square antiprism (J17) structure.[1]

Here, we present a new chapter in this story of this decanuclear cluster. During recent

efforts at preparing and studying the reactions of [Ag3(H)(BH4)L3](BF4), where L =

DPPA = bis(diphenylphosphino)amine, we noticed the formation of colored crystalline

material that turned out to be salts of the related [Ag10(H)8L6]2+ cluster dication.

Gratifyingly, X-ray crystallography revealed the same Ag10 core with a bicapped

square antiprism (J17) structure, although with a different arrangement of the

bisphosphine ligands. Attempts to link the solid-state, solution-phase and gas-phase

structure of [Ag10(H)8L6]2+ will be presented and reactions with relevant

heterocumulenes including CS2 and thiocyanates will be further explored.

References

[1] S. Daly, M. Krstić, A. Giuliani, R. Antoine, L. Nahon, A. Zavras, G. N. Khairallah, V. Bonačić-

Koutecký, P. Dugourd, R. A. J. O’Hair, Phys. Chem. Chem. Phys., 2015, 17, 25772

Oral Presentations


From Reactor to Radiotracer at ANSTO - Increasing the

Availability of Non-routine Radionuclides

Margaret Aulsebrooka*, Leena Hogana, Tom Cresswella, Grant Griffithsa, Attila

Stopica, Ivan Gregurica, Paul Pellegrinia.

aANSTO, New Illawarra Rd, Lucas Heights, NSW 2234, Australia.

Increasing the range and accessibility of radioisotopes is a key objective of the

radioisotopes research team at ANSTO, contributing to the ANSTO Health Strategy

and aligning with ANSTO’s role within the NCRIS National Imaging Facility. The team

has significant experience in the production, separation, purification, characterisation

and formulation of radioisotopes for medical research. Accomplishments include the

development of a (68Ge)/(68Ga) generator for PET imaging,[1-2] the neutron irradiation

and subsequent separation of 177Lu from Yb targets[3-5] and in the high through-put

conversion of (67Ga) gallium citrate to (67Ga) gallium chloride used in phase one clinical

trials targeting prostate cancer.

This talk follows the recent achievements of the radioisotopes team in the delivery of

niche radionuclides to the broader scientific community for the development of new

technologies in medicine, environmental science and fundamental research. Recent

work in the production of non-routine reactor based radioisotopes will be highlighted

with a focus on the therapeutic radionuclide scandium-47 which has recently been

achieved using the OPAL nuclear reactor. Overall, a summary of ANSTO’s recent

efforts to improve access to radioisotopes and radiotracers will be provided along with

a discussion of where this exciting research is heading in the immediate future.

References

[1] Van So, L.; Izard, M.; Pellegrini, P.; Zaw, M., Development of 68Ga Generator at ANSTO: 1st World

Congress on Ga-68 and Peptide Receptor Radionuclide Therapy, THERANOSTICS, Bad Berka,

Germany, June 23-26, 2011, P-023.

[2] Le V.S., 68Ga Generator Integrated System: Elution–Purification–Concentration Integration. In

Theranostics, Gallium-68, and Other Radionuclides. Recent Results in Cancer Research Vol. 194 (eds.

Baum R., Rösch F.) 43-75 (Springer-Verlag, Berlin, Heidelberg 2013).

[3] Van So, L.; Morcos, N., New SPE column packing material: Retention assessment method and its

application for the radionuclide chromatographic separation. Journal of Radioanalytical and Nuclear

Chemistry 2008, 277 (3), 651.

[4] Van So, L.; Morcos, N.; Zaw, M.; Pellegrini, P.; Greguric, I., Alternative chromatographic processes

for no-carrier added 177Lu radioisotope separation Part I. Multi-column chromatographic for clinically

applicable. Journal of Radioanalytical and Nuclear Chemistry 2008, 277 (3), 663.

[5] Van So, L.; Morcos, N.; Zaw, M.; Pellegrini, P.; Greguric, I., Nevissi, A., Alternative

chromatographic process for no-carrier added 177Lu radioisotope separation. Part II. The

conventional column chromatographic separation combined with HPLC for high purity. Journal of

Radioanalytical and Nuclear Chemistry 2008, 277(3), 675.

Oral Presentations


Robust and Recyclable Hybrid Rhodium- and Iridium-

Catalysts with Long Alkyl Tethers

Max Roemer1, Vinicius R. Goncales2, Mohan Bhadbhade2, Barbara A. Messerle1*

1Macquarie University, NSW 2109, Australia, 2 UNSW, NSW 2052, Australia

Transition-metal catalysis is ubiquitous in synthetic chemistry and is among the most

important processes in the chemical industry. Surface immobilised transition metal

catalysts are known as hybrid catalysts as they combine the efficiency of

heterogeneous- and the selectivity of homogenous catalysts. Advantages to the

traditional homogeneous analogues are stability and simplified removal of the catalyst

from the reaction mixture, which provides access to urgently needed more efficient

and greener processes.[1] Here, we present a series of new hybrid Rh- and Ir-based

pyrazole-triazole complexes attached to carbon black (CB) with varying tether length.

The catalysts are composed of a surface anchoring group, an alkyl linker and the

catalytically active metal complex as head group. The synthesis was accomplished

through the high yield alkyl group introduction to aromatic systems[2,3], Click-chemistry

and finally, metal coordination. The length of the alkyl linker (n = 5, 10) was varied to

probe its influence on the catalytic activity. We immobilised the Ir- or Rh-catalysts on

CB using radical methodology. Initially, we optimised grafting conditions to achieve a

dense packing. Furthermore, we attached both, Rh- and Ir-catalysts, in equimolar

amounts simultaneously to achieve a mixed layer. We analysed the modified surfaces

by SEM, EDS and XPS. Subsequently, we tested the systems in an intramolecular

hydroamination reaction. All hybrids are efficient catalysts, which are robust and

recyclable. Intriguingly, the mixed Rh- and Ir-systems perform significantly better than

the monometallic ones, which was already observed for short-chain analogues.[4] We

are currently investigating the origin of this effect.

Fig. 1. a) A mixed Rh- and Ir-hybrid catalyst, b) Intramolecular hydroamination reaction as model

reaction for testing of the hybrid catalysts, c) Molecular structure derived from X-ray single crystal

diffraction of a long alkyl chain ligand.

References:

[1] Wong et al. Chem. Sci. 2016, 7, 1996–2004.

[2] Chen & Roemer et al. Nature Nanotech. 2017, 12, 797–803.

[3] Roemer et al. Eur. J. Inorg. Chem. 2016, 1314–1318.

[4] Binding et al. Organometallics 2019, 38 (4), pp 780–787.

a) b)

c)

N

N N

N

N

O

Rh

n

Carbon Black (CB)

CO

CO

N

N N

N

N

O

Ir

n

Cp*

Cl

NH2

toluene120 °C

NH

catalyst

OH OHhybrid

Oral Presentations


An Exploration into the synthesis and microbial activity of

some heterocyclic bismuth-based complexes

Sarmishta Munuganti*, Philip C. Andrews, Melissa Werrett


Over the last 20 years, the emergence of opportunistic microbial pathogens within

hospital environments has increased the incidence of bloodstream infections, primarily

in immunocompromised individuals.[1],[2] The triazole class of compounds have been

shown to display biological activity against fungal infection and are thus a continuing

area of research interest.

General scheme for the synthesis of novel tris- Bi(III)-1,2,4-triazoles derived from thiones.

The potential of binding these molecules to a bismuth metal centre has been explored

to enhance the biological activity of the ligand(s). A series of novel bismuth(III)-1,2,4-

triazole complexes derived from the general structures 5-(Pyridin-4-yl)-4-phenyl-2H-

1,2,4-triazole-3(4H)-thione have been synthesised.

These complexes have been characterised using 1H NMR and 13C NMR spectroscopy,

IR, ESI-MS and elemental analysis. Fungal testing against the strains saccharomyces

cerevisiae (S. cerevisiae) and candida albicans (C. albicans) are currently underway.

References

[1] M. K. Kathiravan, A. B. Salake, A. S. Chothe, P. B. Dudhe, R. P. Watode, M. S. Mukta and S. Gadhwe, Bioorganic Med. Chem., 2012, 20, 5678–5698.

[2] G. Morace, F. Perdoni and E. Borghi, J. Glob. Antimicrob. Resist., 2014, 2, 254–259.

Oral Presentations


A convenient method for the generation of [Rh(PNP)]+ and

[Rh(PONOP)]+ fragments: reversible formation of

vinylidene derivatives

Matthew R. Gyton, Thomas M. Hood, Adrian B. Chaplin*

Department of Chemistry, University of Warwick, UK

Rigid mer-tridentate “pincer” ligands are a prominent ligand class in organometallic

chemistry and catalysis, conferring thermal stability and enabling a wide range of

metal-based reactivity.[1] Pyridinyl-based phosphine variants, 2,6-bis(di-tert-

butylphosphinomethyl)pyridine and 2,6-bis(di-tert-butylphosphinito)pyridine, in

particular have proven to be versatile ligands and have been employed widely in

homogenous catalysis. Herein we report an operationally simple method for the

generation of reactive formally 14 VE rhodium(I) derivatives (1A) of these ligands in

solution, exploiting substitution reactions of [Rh(COD)2][BArF4] in the weakly

coordinating solvent 1,2-C6H4F2.[2] Application of this methodology enables the

synthesis of known adducts of CO, N2, H2, previously unknown water complexes, and

novel vinylidene derivatives [Rh(pincer)(CCHR)][BArF4] (R = tBu, 3,5-tBu2C6H3),

through reversible reactions with terminal alkynes.[3]

Figure 1. Phosphine-based pincer complexes of rhodium (X = O, CH2)

References

[1] a) D. Morales-Morales, C. G. M. Jensen, Eds., The Chemistry of Pincer Compounds, Elsevier,

Amsterdam, 2007. b) G. van Koten, D. Milstein, Eds., Organometallic Pincer Chemistry, Springer Berlin

Heidelberg, Berlin, 2013.

[2] S. D. Pike, M. R. Crimmin, A. B. Chaplin. Chem. Commun., 2017, 53, 3615–3633.

[3] M. R. Gyton, T. M. Hood, A. B. Chaplin, Dalton Trans., 2019, 48, 2877–2880.

Oral Presentations


Heteroatom-Bridged Transition-Metal Carbynes

Benjamin J. Frogley, Anthony F. Hill*


Transition-metal carbyne complexes, LnM≡CR, have historically been limited to

examples bearing hydrocarbyl (R = alkyl, aryl, etc.), amino or silyl substituents, a

consequence of the classical synthetic pathways not being extendable to the rest of

the p-block.1 Synthetic challenges notwithstanding, there is a strong incentive to

investigate such compounds due to their potentially useful synthetic, electronic and

physical properties which may be modified by the choice of p-block substituent.

Lalor’s bromocarbynes [M(≡CBr)(CO)2(Tp*)] (M = Mo, W; Tp* = hydrotris(3,5-

dimethylpyrazol-1-yl)borate)2 have proven to be useful precursors to such species.

Derivatives can be prepared not only by simple nucleophilic halide substitution, but

also by initial treatment with nBuLi to generate lithiocarbyne intermediates,

[M(≡CLi)(CO)2(Tp*)], which can subsequently react with suitable electrophiles. This

latter procedure allowed the first examples of carbynes with ‘heavy-metalloid’ lead,3

antimony and bismuth substituents4 to be prepared. Extension of this chemistry can

give rise to polymetallic derivatives5 which may serve as useful building blocks for

extended frameworks or interrupted molecular wires. This has particularly interesting

consequences for intermetallic electronic communication where the heteroatoms may

serve as modulators or ‘switches’ in such structures.

References

1. (a) E. O. Fischer, G. Kreis, C. G. Kreiter, J. Müller, G. Huttner and H. Lorenz, Angew. Chem. Int.

Ed., 1973, 12, 564-565; (b) R. R. Schrock, Chem. Commun., 2005, 2773-2777.

2. F. J. Lalor, T. J. Desmond, G. M. Cotter, C. A. Shanahan, G. Ferguson, M. Parvez and B. Ruhl, J.

Chem. Soc., Dalton Trans., 1995, 1709-1726.

3. R. L. Cordiner, A. F. Hill, R. Shang and A. C. Willis, Organometallics, 2011, 30, 139-144.

4. B. J. Frogley and A. F. Hill, Chem. Commun., 2018, 54, 2126-2129.

5. (a) B. J. Frogley and A. F. Hill, Chem. Commun., 2018, 54, 7649-7652; (b) B. J. Frogley and A. F.

Hill, Chem. Commun., 2018, 54, 12373-12376.

Oral Presentations


Multifunctional Cyclopentadiene Ligands for Theranostic

Approaches with Re and 99mTc

Angelo Freia, Roger Albertob*

aInsitute for Molecular Bioscience, The University of Queensland, Australia

b Department of Chemistry, University of Zurich, Switzerland

The ability to manipulate molecules and their properties at will has been scientists

dream since the dawn of chemistry. Particularly in the field of medicinal chemistry it

has been shown again and again, that very small changes can have a dramatic impact

on the biological behaviour of a lead compound. 99mTc is one of the staple

radionuclides for SPECT imaging in the clinic, being used in over 80% of all diagnostic

nuclear imaging studies.1 This is mainly due to the artificial elements favourable

properties and its widespread availability at modest cost. However, current 99mTc

tracers lack the high degree of target specificity that is desired in today’s clinical

applications. Using the cyclopentadiene (Cp) synthon, we have developed a synthetic

approach to multifunctional Cp-Re/99mTc complexes. In this system, the targeting, as

well as other physical and chemical properties of the system can be manipulated

before and after coordination to the metal center. We will report on the chemical

flexibility of this approach as well as the mono- and bi-functionalization of these Cp-

ligands with the synthesis of their respective Re/99mTc complexes. Finally, we will show

how we have used this synthetic toolkit for both conjugated and integrated approaches

preparing new potential theranostic agents with Re and 99mTc.

References

[1] I. Amato, Chem. Eng. News 2009, 87, 58–64. [2] C. Kluba and T. Mindt, Molecules 2013, 18, 3206. [3] A. Frei, B. Spingler, R. Alberto, Chem. Eur. J. 2018, 24, 10156.

Oral Presentations


Palladium-Catalyzed Decarbonylative Trifluoromethylation

of Acid Fluorides

Sinead T. Keaveney†‡ and Franziska Schoenebeck†*

†Institute of Organic Chemistry, RWTH Aachen University, Germany ‡Current: Department of Molecular Sciences, Macquarie University, Australia

Carboxylic acids, and their derivatives, are attractive functionalities for synthetic

manipulations due to their abundance and low cost, and as they can be obtained from

sustainable resources.[1] To further utilize these feedstock chemicals there is a need

to develop strategies to convert carboxylic acids into high value functional groups, with

fluorine being of particular interest due to the numerous applications of organo-fluorine

compounds in the pharmaceutical and agrochemical industries. Further, the

introduction of CF3 via Pd(0)/Pd(II) catalysis is one of the greatest challenges in the

cross-coupling arena due to: i) the difficult reductive elimination of Ar-CF3 from Pd(II);

and ii) the challenging transmetalation of CF3 requires F- additives which can cause

ligand displacement, catalyst decomposition and over-trifluoromethylation.[2] In this

work[3] we overcame these challenges by developing the first protocol to convert acid

fluorides to aryl-CF3, with the key Pd(II)-F intermediate facilitating selective and

additive-free transmetalation, allowing the first use of Xantphos in catalytic

trifluoromethylation. Our computational and experimental reactivity data support a

transmetalation then decarbonylation mechanism.

References

[1] a) R. Takise, K. Muto, J. Yamaguchi, Chem. Soc. Rev. 2017, 46, 5864; b) N.Rodrguez, L. J.

Goossen, Chem. Soc. Rev. 2011, 40, 5030

[2] V. V. Grushin, W. J. Marshall, J. Am. Chem. Soc. 2006, 128, 4632; V. V. Grushin, W. J. Marshall, J.

Am. Chem. Soc. 2006, 128, 12644; Tomashenko, O. A.; Grushin, V. V., Chem. Rev. 2011, 111, 4475;

M. C. Nielsen, K. J. Bonney, F. Schoenebeck, Angew. Chem. Int. Ed. 2014, 53, 5903

[3] Keaveney, S. T.; Schoenebeck, F., Angew. Chem. Int. Ed. 2018, 57, 4073

§ Intramoleculer Pd(II)-F generation

§ Direct transmetalation: no ligand

displacement or over-trifluoromethylation

§ First catalytic effectiveness of Xantphos § Decarbonylation from PhCO-[Pd(II)]-CF3

more facile than that from PhCO-[Pd(II)]-F

17.4 kcal mol-1

27.3 kcal mol-1

Pd

O Ph

CF3PP

Pd

OPh

FP

P

Pd

O Ph

CF3PP

Pd

OPh

FP

P

vs

via:

PdCF3

ArPd

CF3

Ar

O

CO

F

O

R

CF3

R

[Pd(0)]/Xantphos

TESCF3K3PO4 (0.2 eq.)

P

P

P

P

Oral Presentations


Synthesis of difluorogold(III) complexes supported by

N-ligands

Mohammad Al Bayer, Jason L. Dutton(s)*

Department of Chemistry and Physics, La Trobe University

Well defined organometallic or coordination compounds of Au(III)-fluorides are

exceedingly rare.[1,2] Synthesis of difluorogold(III) complexes supported by N-ligands

(pyridine, 4-DMAP and N-methylimidazole) can be achieved by either reacting XeF2

with Au(I) precursors or from tricationic Au(III) precursors by displacement of the N-

ligands using fluoride from economical KF. The new Au(III) complexes were

structurally characterized by single crystal X-ray diffraction, mass spectrometry and

NMR spectroscopy.

References

[1] R. Kumar, A. Linden, C. Nevado, J. Am. Chem. Soc., 2016, 138, 13790.

[2] M. S. Winstron, W. J. Wolf, F. D. Toste, J. Am. Chem. Soc., 2015, 137, 7921.

Oral Presentations


Insights into the s-Block Metalations of Allylic Phosphines

and Phosphine Oxides

Nimrod M. Eren, Emily Border, Victoria L. Blair*


Functionalised nitrogen-based systems are crucial as pharmaceuticals,[1] many of

which are formed using organoalkali reagents. However, phosphorus analogues have

not been studied to the same degree, making their synthetic potential through

organoalkali reactions a key topic.

Our group has focused on the comparative metalation studies of allylic-phosphine and

–amine substrates with organolithium and organosodium reagents. Through structural

and solution state studies we have revealed structural-reactivity dependence, from

both donor ligand denticity[2] and allylic chain composition. Extending this study to the

pentavalent phosphorus oxidation state, has allowed the structural elucidation of a

range of allylic anionic phosphine oxides to be characterised revealing ‘Wittig type’

intermediates when their reactivity was probed.

Figure 1: Structural diversity in lithiated allylic phosphine oxides

References

[1] E. Vitaku, D. T. Smith, J. T. Njardarson, Journal of Medicinal Chemistry 2014, 57, 10257-10274. [2] V. L. Blair, M. A. Stevens, C. D. Thompson, Chemical Communications 2016, 52, 8111-8114.

Oral Presentations


Anti-Leishmanial Activity of Organometallic Antimony (V) And Gallium (III) Quinolinolato Complexes

Rebekah N Duffin*, Victoria L Blair, Lukasz Kedzierski and Philip C Andrews

School of Chemistry, Monash University, Australia

The prevalence of neglected tropical diseases is on the rise, with the parasitic ailment

leishmaniasis being no exception. Its locality in 90+ tropical/sub-tropical low

socioeconomic countries and increased cases of established drug resistance, makes

the design and characterisation of new potentially low-cost drug candidates a high

priority.1, 2 Previous studies by Andrews et al had focused primarily on aryl complexes

of the group 15 metal antimony,3 due to the similarities with the current front-line

treatment, however recent investigations into the medicinally relevant gallium has

revealed a whole new potential in the world of organometallic medicinals. Gallium has

shown previous applications in radiopharmaceuticals, anti-cancer agents and a

varying degree of bactericides, but little has been explored in the ways of anti-

parasitics.4 Utilising the medicinally5 and fluorescently active class of 8-hydroxy-

halido-quinolinols, 8 gallium complexes and 6 antimony complexes, were successfully

synthesised and characterised (figure 1), eleven of which have been evaluated for

their anti-leishmanial activity.

References

[1] W. H. Organization, Investing to Overcome the Global Impact of Neglected Tropical Diseases: Third WHO Report on Neglected Tropical Diseases 2015, World Health Organization, 2015.

[2] A. Ponte-Sucre, F. Gamarro, J.-C. Dujardin, M. P. Barrett, R. López-Vélez, R. García-Hernández, A. W. Pountain, R. Mwenechanya and B. Papadopoulou, PLoS Negl. Trop. Dis., 2017, 11, e0006052.

[3] R. N. Duffin, V. L. Blair, L. Kedzierski and P. C. Andrews, Dalton Trans., 2018, 47, 971-980.

[4] F. Minandri, C. Bonchi, E. Frangipani, F. Imperi and P. Visca, Future Microbiol., 2014, 9, 379-397.

[5] M. C. Duarte, L. M. dos Reis Lage, D. P. Lage, J. T. Mesquita, B. C. S. Salles, S. N. Lavorato, D. Menezes-Souza, B. M. Roatt, R. J. Alves and C. A. P. Tavares, Vet. Parasitol., 2016, 217, 81-88.

Figure 1. X-ray structures of the complexes [GaMe(C9H4ONCl2)2] and

[Ga(Me2)C9H4ONCl2]

Oral Presentations


Tunable Photoluminescent Properties of a New Class of

Thermally Robust Monocyclometalated Gold(III)

Complexes

Robert Malmberg, Koushik Venkatesan*

Department of Molecular Sciences, Macquarie University, NSW 2109, Australia

Phosphorescent gold(III) complexes and their possible applications in optoelectronic

devices have gained an increased interest.[1] Our group has studied Au(III) based

monocyclometalated complexes bearing diaryl or dialkyne ancillary ligands exhibiting

room temperature emission in solution, solid state and in PMMA thin films.[2] It was

shown that the emission profile can be tuned by employing different

monocyclometalated ligand frameworks to achieve emission colours covering the

visible spectrum. Although there was a strong correlation of the photoluminescent

quantum yields (em) and the triplet excited state lifetimes (0) on the kind of

monocyclometalated ligand as well as the ancillary ligands, the ancillary ligands

utilized thus far were limited to monodentate ligands. In order to improve the excited

state properties of monocyclometalated complexes, a new structural design was

sought, in which the ancillary ligands were replaced with bidentate ligands.

Herein, we present the synthesis and luminescent properties of two classes of

thermally robust monocyclometalated gold(III) complexes with new ancillary bidentate

ligands that have a dramatic influence on the em and 0.[3] These results are expected

to further contribute to strategies for the deployment of Au(III) complexes as emitter

molecules in phosphorescent organic light emitting diodes (PhOLEDs).

[1] V. W.-W. Yam, E. C.-C. Cheng, Chem. Soc. Rev. 2008, 37, 1806-1806; b) G. Cheng, K. T. Chan, W. P. To, C. M. Che, Adv. Mater. 2014, 26, 2540-2546; c) R. Kumar, A. Linden, C. Nevado, Angew. Chem. Int. Ed. 2015, 54, 14287-14290.

[2] T. von Arx, A. Szentkuti, T. N. Zehnder, O. Blacque, K. Venkatesan, J. Mater. Chem. C 2017, 5, 3765-3769; b) J. A. Garg, O. Blacque, T. Fox, K. Venkatesan, Inorg. Chem. 2010, 49, 11463-11472.

[3] R. Malmberg, M. Bachmann, O. Blacque, K. Venkatesan, Chem. Eur. J. 2019, 25, 3627-3636.

Oral Presentations


Reactions of Planar-Chiral 1-P(S)Ph2-2-CH2OH Ferrocenes

Marcus Korb,a* Julia Mahrholdt,b Xianming Liu,b and Heinrich Langb

a School of Molecular Sciences, The University of Western Australia, Perth, Australia

b Inorganic Chemistry, TU Chemnitz, Germany

Ferrocenyl phosphines are prominent planar-chiral ligands in e.g. Pd-catalyzed

reactions. It has been shown that the introduction of weakly coordinating ortho

substituents, such as vinyl groups and ether functionalities, stabilize the catalytically

active species and increase the productivity and activity.[1] However, to use 1-PPh2-2-

OMe-Fc motif (1), obtained via anionic phospho-Fries reactions,[2] in asymmetric

transformations, results in a low ee within biaryl coupling products.[3]

In the search for better enantioselective catalytic performance, derivatives of 1-

P(S)Ph2-CH2OH-Fc (2) have been explored. However, exchange of the OH

functionality occurs under various conditions, with migration of the sulfur atom towards

the α-CH2-group under mild conditions (Figure 1).[4] The application of the resulting

compounds as ligands within Suzuki-Miyaura reactions for sterically hindered biaryls

is presented, where an ee of up to 69 % could be obtained.

Figure 1. Reaction behaviour of CH2-enlarged P,O-ferrocene (Sp)-2. (a) Based on the formation of triple-

ortho-substituted biaryls within a Pd-catalyzed Suzuki-Miyaura C,C cross-coupling reaction.)

References

[1] D. Schaarschmidt, H. Lang, ACS Catal. 2011, 1, 411–416. [2] M. Korb, D. Schaarschmidt, H. Lang,

Organometallics 2014, 33, 2099–2108; M. Korb, H. Lang, Organometallics 2014, 33, 6643–6659. [3]

M. Korb, H. Lang, Chem. Soc. Rev. 2019, DOI: 10.1039/c8cs00830b. [4] M. Korb, J. Mahrholdt, X. Liu,

H. Lang, Eur. J. Inorg. Chem. 2019, 973–987

Oral Presentations


Metal Complexes for Molecular Electronics: Explorations

of Thioether Anchor Groups

M. Naher,a D. Costa Milan,b I. Planje,b S.J. Higgins,b R.J. Nichols,b P. J. Lowa,*

a School of Molecular Sciences, University of Western Australia

b Department of Chemistry, University of Liverpool

The design and preparation of efficient ‘molecular wires’ that allow the study of charge

transport through electrode|molecule|electrode junctions is of primary interest for the

development of novel molecular electronics and molecular electronic materials.

However, to measure, and ultimately control, electron transport through a molecular

junction one must not only synthesize molecules with desired functions embedded in

the backbone, but also design proper molecule-electrode contacts.

Here we describe the syntheses and electronic properties of a novel series of organic

and organometallic compounds bearing thiomethyl and 3,3-dimethyl-2,3-

dihydrobenzo[b]thiophene (DMBT) functionalities as two different anchor group. The

effects that arise from variation of conjugated backbone structure, the thioether

contacting groups and the metal ancillary ligands (L) on the electronic structure,

spectroscopic properties, chemical reactivity, and behaviour in metal|molecule|metal

junctions will be discussed. In particular, the performance of the thiomethyl and DMBT

functional groups as surface binding moieties, as evaluated within scanning tunneling

microscope break-junction (STM-BJ) and STM based current distance (STM-I(s))

molecular junctions will be presented.

Oral Presentations


Ligand Exchange Reaction and Catalysis of the Conversion of Cyanide and Thiosulfate to Thiocyanate and

Sulfite by a Molybdenum Complex

Sigridur G. Suman1*, Johanna M. Gretarsdottir1

1Science Institute, University of Iceland, Dunhagi 3, 107 Reykjavik, Iceland.

Enzyme catalyzed conversion of cyanide and thiosulfate to thiocyanate and sulfite is well documented [1]. The reaction is metal-free employing rhodanase enzyme. Formation of thiocyanate in the spontaneous reaction of cyanide and sulfur is slow [2]. A few examples are known of cyanide forming thiocyanate when reacting with sulfur bound to molybdenum enzymes [3]. Fewer still examples are known of cyanide forming thiocyanate in a reaction of molybdenum complexes with cyanide [4]. Cyanide easily displaces the DMF ligands of the Mo2O2S4(DMF)3 complex as well as reacts with the disulfide ligand on the complex in a sulfur abstraction reaction [5]. One to three DMF ligands are displaced by cyanide in the exchange reaction to potentially form several different products. The products from the exchange reaction were analyzed to determine the preferred product as (a) the products from the exchange reaction or (b) the products from a sulfur abstraction reaction.

The reactivity of the sulfur abstraction reaction by cyanide with the disulfide to form thiocyanate was studied stoichiometrically as a function of pH. High conversion of cyanide to thiocyanate was achieved in a time period of 20 minutes. Reaction mechanism of the catalytic reaction was investigated experimentally and with DFT calculations.

Catalytic cycle is proposed where initial step requires a sulfur abstraction reaction. Potential deactivation routes of the catalytic cycle were discovered when a catalytically inactive complex was isolated and characterized.

Financial support by the Icelandic Centre of Research grant nr 140945 is gratefully acknowledged.

References

[1] K. R. Leininger, J. W., The Mechanism of the Rhodanese-catalyzed Thiosulfate Cyanide Reaction. J. Biol. Chem. 1967, 243 (April 25), pp. 1892-1899.

[2] David R. Singleton, D. W. S., Improved Assay for Rhodanese in Thiobacillus spp. Appl. Environ. Microbiol., Nov. 1988, pp. 2866--2867.

[3] R. Hille, Molybdenum-containing hydroxylases. Arch Biochem Biophys 2005, 433 (1), pp. 107-116. [4] R. S. Pilato, E. I. Stiefel, Inorganic Catalysis, 2nd ed.; Reedijk, J., Bouwman, E., Eds.; Marcel

Dekker: New York, 1999; pp. 81-152. [5] J. H. Enemark, C. G. Young, Bioinorganic Chemistry of Pterin Containing Molybdenum and

Tungsten Enzymes, Adv. Inorg. Chem. 1993, 40, pp. 1-88. [6] C. G. Young, Models for the molybdenum hydroxylases J. Biol. Inorg. Chem. 1997, 2, pp. 810-816. [7] P. D. Smith, D. A. Slizys, G. N. George, C. G. Young, Toward a Total Model for the Molybdenum

Hydroxylases: Synthesis, Redox, and Biomimetic Chemistry of Oxo-thio-Mo(VI) and -Mo(V) Complexes. J. Am. Chem. Soc. 2000, 122, pp. 2946-2947.

[8] J. M. Gretarsdottir, “Syntheses of new molybdenum-sulfur complexes: Catalytic transformation of cyanide to thiocyanate and in vitro biological studies“, PhD Thesis, University of Iceland, 2018.

Oral Presentations


Rhodium (I)-Vinyl Complexes as Effective Initiators in the

Stereospecific Polymerization of Phenylacetylene

Nicholas Tan 1*, Mark I. Ogden1, Massimiliano Massi1, Andrew B. Lowe1

1Curtin Institute for Functional Molecules and Interfaces (CIFMI), School of Molecular

Life Sciences, Curtin University, Perth, Australia

Rh(I) complexes are well known to mediate polymerization of arylacetylenes such as

phenylacetylene as a route to functional materials. The importance of such materials

are largely due to their optoelectronic properties stemming from the π-conjugated

backbone, and by modification of the side chains useful structural features can be

introduced such as helical conformations which can be applied in stimuli-responsive

materials, gas permeable membrane, molecular recognition, and catalytic studies.

Rh(I)-based complexes are used widely, owing to their low intrinsic oxophilicity,

excellent functional group compatibility and high reactivity towards alkynes. Also,

Rh(I)-based complexes can be effective initiators for the controlled stereospecific

polymerization of substituted arylacetylenes. In this presentation, I present three new

Rh(I)-α-phenylvinylfluorenyl complexes bearing fluorine-functionalised phosphine

ligands, Rh(nbd)(CPh=CFlu)P(4‐FC6H4)3, Rh(nbd)(CPh=CFlu)P(4‐CF3C6H4)3, and

Rh(nbd)(CPh=CFlu)P[3,5‐(CF3)2C6H3]3 (nbd: 2,5‐norbornadiene; Flu: fluorenyl) that

have been evaluated in the stereospecific polymerization of phenylacetylenes[1], with

initiation efficiencies of up to 56 %, yielding low dispersity (Ð = Mw/Mn)

polyphenylacetylenes with high cis-transoidal stereoregularity. In addition, the

controlled-like nature of the polymerization of PA have been demonstrated through the

preparation of block copolymers via sequential monomer addition.

References

[1] Tan, N. S. L. et al. Rhodium(I)-α-Phenylvinylfluorenyl Complexes: Synthesis, Characterization, and Evaluation as Initiators in the Stereospecific Polymerization of Phenylacetylene. Eur. J. Inorg. Chem. 2019, 592–601 (2019).

Oral Presentations


An unprecedented diversity of 1,3-disubstituted ferrocenes

through the halogen ‘dance’ reaction

W. Erb, M. Tazi, K. Al-Mekhlafi, Y. S. Halauko, O. A. Ivashkevich, V. E. Matulis, T.

Roisnel, V. Dorcet, F. Mongin

Institut des Sciences Chimiques de Rennes, Université de Rennes 1

Since its discovery by Miller and Pauson and structure elucidation by Woodward,

Wilkinson and Fisher, ferrocene has always drawn the attention of the chemists

community.1 Therefore, due to its specific properties, it is currently hard to find an area

of chemistry free of ferrocene derivatives.

However, the field remains dominated by monosubstituted, 1,1’- and 1,2-disubstituted

derivatives which can be easily prepared by using aromatic electrophilic substitution

or deprotometallation followed by electrophilic trapping. In sharp contrast, the

chemistry of 1,3-disusbtituted ferrocenes remains by far less explored although

promising applications are reported due to the large angle between the two

substitutents.2 This results from the lack of easy and general syntheses of these

derivatives.

Here, we will show how the halogen ‘dance’ reaction, a stability driven reaction, can

be used as a key step to access 1,3-disubstituted ferrocene derivatives.3 An efficient

control of the reaction outcome can be reached through the careful choice of directing

and protective group (DG and PG, respectively) and pave the way toward highly

functionalized ferrocene compounds.

References

[1] (a) T. J. Kealy, P. L. Pauson, Nature 1951, 168, 1039; (b) S. A. Miller, J. A. Tebboth, J. F. Tremaine, J. Chem. Soc. 1952, 632; (c) Ferrocenes: Ligands, Materials and Biomolecules; Eds. P. Stepnicka; Wiley: Hoboken, NJ, 2008.

[2] (a) T. Muraoka, K. Kinbara, T. Aida, Nature 2006, 440, 512; (b) J. Y. C. Lim, P. D. Beer, Eur. J.

Inorg. Chem. 2017, 2017, 220.

[3] (a) M. Tazi, W. Erb, Y. S. Halauko, O. A. Ivashkevich, V. E. Matulis, T. Roisnel, V. Dorcet, F.

Mongin, Organometallics, 2017, 36, 4770; (b) M. Tazi, M. Hedidi, W. Erb, Y. S. Halauko, O. A.

Ivashkevich, V. E. Matulis, T. Roisnel, V. Dorcet, G. Bentabed-Ababsa, F. Mongin,

Organometallics, 2018, 37, 2207.

Oral Presentations


Direct reaction—a simple route to synthesis

organoioamidodidolanthanoid(II/III) complexes

Zhifang Guo, Victoria Blair, Glen B. Deacon*, Peter C. Junk*

School of Chemistry, Monash University, Clayton 3800, Australia.

College of Science & Engineering, James Cook University, Townsville 4811, Qld,

Australia.

Heteroleptic lanthanoid(II/III) metal-organic compounds, including hydrides, amides,

alkoxides, aryloxides, cyclopentadienyls have been synthesized from sources of

LnLX2, LnL2X, LnLX (X = halide). [1] Suitable rare earth reactants [Ln(L)nX3-n] (X = Cl,

Br, I) have been widely prepared by metathesis reactions. However, metathesis

syntheses of [Ln(L)nX3-n] (or [LnLX]) have potential rearrangement outcomes. This

report describes a simple method—direct reaction (an effective, metal-based route) to

obtain a number of lanthanoid complexes [Ln(L)nI3-n] with high yields, from excess of

metals with iodine and ligand in thf.

[Ln(DFForm)2I(thf)2] [Ln(DFForm)I2(thf)3] [Ln(DippForm)I2(thf)3] [Ln(Me2pz)I2(thf)3] [Ln(Me2pz)I2(thf)4]

References

[1]. (a) R. Duchateau, C. T. van Wee, A. Meetsma, J. H. Teuben, J. Am. Chem. Soc., 1993, 115,

4931-4932; (b) J. W. Evans, R. A. Keyer, J. W. Ziller, Organometallics, 1993, 12, 2618-2633;

(c) P. B. Hitchcock, S. A. Holmes, M. F. Lappert, S. Tian, Chem. Commun., 1994, 2691-2692;

(d) W. J. Evans, R. N. R. Broomhall-Dillard, J. W. Ziller, Organometallics, 1996, 15, 1351; J.

Organomet. Chem., 1998, 569, 89-97; (e) A. A. Trifonov, E. N. Kirillov, A. Fischer, F. T.

Edelmann, M. N. Bochkarev, Chem. Commun., 1999, 2203-2204; (f) H. Schumann, J. A.

Meese-Marktscheffel, L. Esser, Chem. Rev., 1995, 95, 865-986.

LnX3 + n ML Ln(L)nX3-n + n MX (1)

X = halide, Cl, Br, IM = alkali metal, Li, Na, K

2 X2LnL LnL2X + LnX3

1/2 LnL3 + 1/2 X2LnL

(2)

3 LnLnX3-nn LnL3 + (3-n) LnX3 (3)



A Mechanistic Study of Ruthenium (II) Catalysed C-H

Amidation and Thioamidition

W. A. O. Altalhi, A. I. McKay, P. S. Donnelly, A. J. Canty, R. A. J. O’Hair*

School of Chemistry, The University of Melbourne

Amides and thioamides are important functional groups which are widely utilised in the

chemical and pharmaceutical industries. Traditional methods for their syntheses suffer

from poor atom economy (stoichiometric amounts of waste) and tedious

prefunctionalisation.[1] New efficient methods for amide synthesis involving the

insertion of an isocyanate into a C-H bond have been recently reported.[2]

Unfortunately, most of studies can be classified as “black box” since they typically

feature complicated cocktails of additives and solvents and their underlying

importance with regards the proposed catalytic cycle is rarely explained.

In this study, we use a combination of gas-phase and solution experiments together

with DFT calculations to investigate the mechanism of Ruthenium (II) catalysed C-H

amidation of N,N’-dimethylbenzylamine. This substrate presents an attractive target

as amide synthesis has already been reported by ortholithiation, phenyl isocyanate

insertion, followed by hydrolysis.[3] We isolate and crystallographically characterise a

key C-H activated intermediate and study its reactivity with a range of alkyl- and aryl

isocyanates both in solution and the gas phase using ESI-MS. Other key steps of the

mechanism have also been examined, as well as attempts to develop C-H

thioamidation protocols.

References

[1] Bode, J.W., et. al. Nature, 2011, 480, 471-479.

[2] Cheng, C.-H.; et. al., Org. Lett., 2012, 14, 4262-4265.

[3] Hauser, C.R.; et. al., J. Org. Chem., 1963, 28, 3461-3465.

C

N

N

H

O H



Charting the Reaction Coordinate in ‘Beryllocene’

Stephen P Best,1* Albert Paparo,2 Courtney Ennis,3

1 School of Chemistry, The University of Melbourne, 2 School of Chemistry Monash

University, 3 School of Chemistry, Otago University.

We aim to establish the framework for the interpretation of the vibrational spectra of

dynamic molecules. This contribution focuses on ‘beryllocene’, 5, 1-Be(C5H5)2 – Bc,

a dynamic molecule with activation energies below ca. 8 kJ mol-1 [1]. Molecular

mechanics and theory are broadly in line with these conclusions [2] and a measure of

the dynamic behaviour of the molecule at RT is evident from comparison of the 298

and 173 K X-ray structures shown below. In addition to the large increase in the

thermal ellipsoids, the centroid positions are drawn indicating a 2, 5 geometry. This

is the computed transition state for rotation of the 1-bound ring.

We have recently shown that the temperature dependence of the IR spectra can be

used to chart the reaction coordinate for interconversion between rotamers of

ferrocene (Fc) and that medium-dependent differences in the activation energy lead

to differences in the band profile for Fc in its different states [3]. In this contribution we

outline our recent studies into the extension of the dynamic vibrational spectroscopic

approach to Bc. Comparatively simple measures of the temperature dependence of

the vibrational spectra have the potential to provide direct experimental measures of

the reaction coordinate and barrier for dynamic molecules and with it to provide

important insights into reaction dynamics more generally.

X-ray structures of Bc at 173 K (left) and 298 K (right) [1c]. Thermal elipsoids are drawn at the 50%

probability level.

References

[1] a. K. W. Nugent, J. K. Beattie, J. Chem. Soc., Chem. Commun. 1986, 186-187; b. K. W. Nugent, J. K. Beattie, L. D. Field, J. Phys. Chem. 1989, 93, 5371-5377; c. I. Hung, C. L. B. Macdonald, R. W. Schurko, Chem. - Eur. J. 2004, 10, 5923-5935.

[2] P. Margl, K. Schwarz, P. E. Bloechl, J. Am. Chem. Soc. 1994, 116, 11177-11178. [3] S. P. Best, F. Wang, M. T. Islam, S. Islam, D. Appadoo, R. M. Trevorah, C. T. Chantler, Chem.

Eur. J. 2016, 22, 18019-18026.



Alkynyltellurolate Ligands and a Solvatochromic

Rhenium(I) Complex

Liam K. Burt, Anthony F. Hill*

ANU Research School of Chemistry, Australian National University

Sullivans Creek Road, Acton, ACT, 2601

[email protected]

Organotellurium metal complexes remain scarce in the literature despite growth in

recent years. These tellurium-based ligands are classified as telluroethers (R–Te–R),

tellurolates (RTe– + M’) or tellurides (Te2–) depending on the binding mode to the metal

centre. Rare complexes featuring tellurolate ligands have been flagged as highly

unstable due to air sensitivity, diffusive sets of orbitals and further reactivity.

This work presents the first examples of alkynyltellurolate complexes as a continuation

of the alkynylselenolate species previously explored.[1] Iron and rhenium-based

species [CpFe(TeCCPh)(CO)(PPh3)] and [(bpy)Re(TeCCSiMe3)(CO)3] were

synthesised via lithiation of an alkyne, chalcogen insertion and subsequent

metathesis.

Further investigation of this alkynyltellurolate rhenium complex revealed interesting

photophysical properties, including visible solvatochromism.

Molecular structure obtained for [(bpy)Re(TeCCSiMe3)(CO)3].

References

[1] Caldwell, L. M., Hill, A. F., Hulkes, A. G., McQueen, C. M. A., White, A. J. P., Williams, D. J.,

Organometallics 2010, 29, 6350.

mailto:[email protected]



Single-Molecule Magnets: Lanthanide - β Diketonates

“Triangles”

Chiara Caporale,a Alexandre N. Sobolev,b Wasinee Phonsri,b Keith S. Murray,b

Massimiliano Massi,a and Rebecca O. Fuller a*

a School of Molecular and Life Science, Curtin University, Bentley, WA

b School of Chemistry, Monash University, Clayton, VIC

c School of Molecular Sciences, The University of Western Australia, Crawley, WA

Single-molecule magnets (SMMs) are being developed as potential components for

information storage.[1] Since the discovery of a dodecanuclear MnIII/MnII acetate

complex,[2] researchers have continued to explore molecules that retain magnetisation

even after the applied field is removed. A large number of different SMMs are being

developed, including those based on homometallic 3d or 4f clusters and heterometallic

3d-4f complexes. Trigonal lanthanide complexes are known to display interesting

magnetic properties.[3] The symmetry and magnetic moment is known to play role in

the observed properties. Our research has focus its attention in the synthesis and

characterisation of lanthanide trinuclear clusters, in order to provide a detailed

knowledge of the structure-properties relationship of these materials and aim to

facilitate the future development of high performance SMMs for the next generation of

devices.

Figure 1: Example of Lanthanide - β Diketonates “triangle”

References

[1] Feltham, H. L. C.; Brooker, S., Coord. Chem. Rev, 2014, 276, 1.

[2] Sessoli, R; Tsai, H. L.; Schake, A. R. et al., J. Am. Chem. Soc., 1993, 115, 1804.

[3] L. F. Chibotaru, L. Ungur, A. Soncini, Angew. Chem. Int. Ed. 2008, 120, 4194-4197



Use of Ag(C6F5) or Bi(C6F5)3 instead of HgAr2 reagents in

redox transmetallation/protolysis reactions of free

lanthanoid metals

Glen B. Deacon, Zhifang Guo, Jenny Luu, Victoria Blair, Peter C. Junk


College of Science & Engineering, James Cook University, Townsville 4811, Qld,

Australia.

We have established redox transmetallation/protolysis (RTP) reactions of lanthanoid

metals with diarylmercurials and protic agents (phenols, amines, pyrazoles,

formamidines, and cyclopentadienes) to be an effective synthesis of highly reactive

rare earth compounds. [1]

The method is competitive with metathesis, but the synthesis would be more attractive

if a less toxic metal could be employed. We have now examined both AgC6F5 and

Bi(C6F5)3 as alternative reagents. [2, 3]

A new synthesis of AgC6F5 from commercially available, air-stable reagents helps. [2]

Both AgC6F5 and Bi(C6F5)3 have been tested in the synthesis of lanthanoid pyrazolates

for a wide range of Ln metals and several pyrazoles. [2, 3] Both reagents are effective

but have limitations. [4]

References

[1]. (a) G. B. Deacon, C. M. Forsyth, S. Nickel, J. Organomet. Chem., 2002, 647, 50- 60; (b) G. B.

Deacon, Md E. Hossain, P. C. Junk, M. Salehisaki, Coord. Chem. Rev., 2017, 340, 247-265.

[2]. Z. Guo, J. Luu, V. Blair, G. B. Deacon, P. C. Junk. Eur. J. Inorg. Chem., 2019, 1018-1029.

[3]. Z. Guo, V. Blair, G. B. Deacon, P. C. Junk. Chem. Eur. J., 2018, 24, 1-12

[4]. Support of the Australian Research Council and the Australian Synchrotron are gratefully

acknowledged.

Ln + n/2 HgAr2 + n LH Ln(L)n + n/2 Hg + n ArH (1)

n = 2, 3 Ar = C6F5, Ph, CCPh

Ln + 3 AgC6F5 + 3 LH Ln(L)3 + 3 Ag + 3 C6F5H (2)

Ln + Bi(C6F5)3 + 3 LH Ln(L)3 + Bi + 3 C6F5H (3)

Ag2O + 2 C6F5H [Ag2(C6F5)2(py)3] + H2O (4)py



Lewis acids: Versatile catalysts for fundamental

transformations and polymerisations

Deepamali Dissanayake, Siyuan Zhai, Zhizhou Liu, Alysia Draper, William McAllister,

Dragoslav (Drasko) Vidovic*


Recent evidence has suggested that Lewis acid catalysis is underdeveloped due to

inadvertent presence of hidden Bronsted acids. In recent years we have developed

several NacNac-supported aluminium complexes that showed exceptional activity as

Lewis acid catalysts for various Diels-Alder cycloadditions, Michael additions and

borylations.[1] It was also discovered that a very subtle structural modification led to

unprecedented polymerisation of cyclic dienophiles. Lastly, our progress towards

chiral system will also be discussed.

References

[1] a) J. Org. Chem. 2018, 83, 529. b) Dalton Trans. 2017, 46, 753. c) Chem. Eur. J. 2015, 21, 11344.



Optical Nonlinearities of Y-shaped and H-shaped

Arylalkynylruthenium Complexes

Jun Du, Mahbod Morshedi, Mahesh S. Kodikara, Marek Samoc, Marie P. Cifuentes,

Mark G. Humphrey*


Straightforward syntheses of bis[bis{1,2-bis(diphenylphosphino)ethane}ruthenium]-

functionalized1,3,5-triethynylbenzene-cored complexes via a methodology employing

“steric control” permit facile formation of Y-shaped Sonogashira coupling products and

distorted-H-shaped homo-coupled quadrupolar products. The quadratic and cubic

optical nonlinearities were assessed by the hyper-Rayleigh scattering and Z-scan

techniques. The cyclic voltametric data reveal two reversible metal alkyntl-localized

oxidation process for all complexes. Computational studies based on time-dependent

density functional theory were applied to assign the key low-energy transitions in the

linear optical spectra and to compute the quadratic nonlinear optical tensorial

components.



A [3]Rotaxane With Coupled Rotary and Linear Shuttling

Motion

James A. Findlay, James D. Crowley*


Control over molecular motion will have important repercussions throughout

nanotechnology, and this was recognized by the awarding of the 2016 Nobel Prize in

Chemistry “for the design and synthesis of molecular machines”. Research groups,

including Prof. J-P Sauvage’s, have reported switchable catenane and rotaxane-

based molecular machines, taking advantage of the change in coordination preference

of copper ions between the 1+ (usually tetrahedral) and 2+ (5 or 6 coordinate)

oxidation states to alter the position of a macrocycle within mechanically interlocked

architectures (MIAs).1,2 Previously, our lab has reported molecular switches using the

same stimulus to produce rotary motion within non-interlocked ferrocene (Fc)-based

systems.3 The synthesis of a [3]rotaxane is described where a bipyridine (bipy)-

containing macrocycle is mechanically interlocked to each ‘arm’ of a 1,1’-disubstituted

Fc ligand. The two thread ‘arms’ provide both a bidentate and a tridentate coordination

site for binding of Cu(I) and Cu(II) ions with the bipy-macrocycle, respectively. This

design would give rise to redox controlled linear shuttling of the macrocycle along the

thread, simultaneously switching the bidentate chelates of the threads between a π-π

stacked state and being occupied by the sterically demanding macrocycle, causing

rotation about the Fc joint (Figure 1). To the best of our knowledge this would be the

first example of coupled molecular rotary and linear shuttling motions.

References

[1] Durot, S., Reviriego, F., Sauvage, J-P., Dalton Trans., 2010, 39, 10557-10570. [2] Champin, B., Mobian, P., Sauvage, J-P., Chem. Soc. Rev., 2007, 36, 358-366. [3] Scottwell, S. Ø., Elliott, A. B. S., Shaffer, K. J., Nafady, A., McAdam, C. J., Gordon, K. C., Crowley, J. D., Chem. Commun. 2015, 51, 8161. [4] Lewis, J. E. M., Bordoli, R. J., Denis, M., Fletcher, C. J., Galli, M., Neal, E. A., Rochettea, E. M. and Goldup, S. M. Chem. Sci. 2016, 7, 3154.



Bimetallic Group 14 Complexes Stabilised by Bis(N,N’-

diarylamidinate) Ligand

Palak Garg, Cameron Jones*


The last two decades have seen a search for main-group metal complexes as cheaper

and less toxic alternatives to the transition metal complexes in several applications,

e.g. catalysis.1 The tunable steric and electronic properties of amidinate ligands

[RC{NR’}2]- gives kinetic stability to low valent main-group metal complexes. Recently,

bifunctional amidinate ligands have successfully allowed access to unusual rare earth

and group 13 metal complexes.2 Herein, we report the synthesis of group 14 bimetallic

complexes XML-C6H4-LMX (Scheme 1) using salt metathesis reactions. Currently, we

are investigating the possibility of forming bimetallic group 14 hydride complexes. The

bimetallic hydride complexes are expected to possess unique bifunctional catalytic

properties as a result of synergistic effects between adjacent metal centres. The

reduction of these bimetallic complexes may possibly lead to the main group metal

coordinating polymers.

Scheme 1. Synthetic of bimetallic group 14 complexes.

References

[1] Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th Ed.

1999, Wiley, Chichester, United Kingdom.

[2] (a) Li, M.; Hong, J.; Chen, Z.; Zhou, X.; Zhang, L. Dalton trans. 2013, 42, 8288.

(b) Lei, Y.; Chen, F.; Luo, Y.; Xu, P.; Wang, Y.; Zhang, Y. Inorganica Chim. Acta 2011, 368, 179.

HN

N NH

N

R

R

R

R

1. nBuLi, THF

2. MX2, RT N

N N

N

R

R

R

R

MM

X

X

R =

M = Ge, Sn

X = Cl



Antitumor dinuclear platinum (II) complexes with DNA

imbedding groups

Chuanzhu Gaoa*,b*, Tianshuai Wanga, Yan Zhanga, Zhuxin Zhanga, Glen B. Deaconb

aFaculty of Life Science and Technology, Kunming University of Science and Technology, Kunming 650500, China

bSchool of Chemistry, Monash University, Clayton 3800, Australia.

Aromatic groups could embed in grooves of the double helix structure of tumor DNA and act as antitumor drugs such as Mitoxantrone. Some of them have been introduced and linked two trans-1R-2R-cyclohexanediamines(DACH) as bridges, and novel dinuclear platinum complexes have been synthesized and characterized. We hope that the new binuclear platinum complexes can not only overcome cross-

resistance due to their different mononuclear structures from cisplatin, but also play a

synergistic anti-tumor role due to the introduction of DNA embedding groups.

In vitro cytotoxicities of dinuclear platinum complexes against tumor cells were

evaluated using MTT assay. Results indicated that lipid-water partition coefficient has

important influences on the antitumor activity and some of them showed better activity

than oxaliplatin and carboplatin.

References

[1]. C. Yu, C. Gao*, L. Bai, Bioorg. & Med. Chem. Lett., 2017, 27, 963-966.

[2]. Z. Zhang, C. Li, C. Gao*, Inorg. Chim. Acta., 2017, 45,166-172.

[3]. C. Gao*, T. Wang, Y. Zhang, Appl. Organomet. Chem., 2015, 29, 38-142.

[4]. Support of the s National Natural Science Foundation and Doctoral Program of the Ministry of Education of PR China are gratefully acknowledged.



Synthesis and Reactivity of Carbon-Rich and

Cumulenylidene Ligands in Iron and Ruthenium

Complexes

Michael R. Hall, a Rachel R. Steen,a,b Paul J. Low,a and Jason M. Lynamb

a School of Molecular Sciences, University of Western Australia, Perth, Australia

b Department of Chemistry, University of York, York, UK

Carbon-rich ligands currently attract interest for their unusual electronic structures,

having application as components in electronic and optoelectronic devices.[1]

Recently, attention has turned to their use in organic synthesis, with novel aryl-spaced

cumulene ligands being identified as potential reagents for regioselective alkyne

activation.[2] A series of trapping reactions of metallacumulenes containing phenyl and

thienyl spacing units are reported, both from vinylidene and alkynyl precursors.

Figure 1. Dynamic vinylidene – acetylide – cumulene equilibrium

References

[1] Marqués-González, S., & Low, P. J. Aust. J. Chem., 2016, 69(3), 244-253; Garner, M. H., Bro-Jorgensen, W., Pedersen, P. D. & Solomon, G. C. J. Phys. Chem. C., 2018, 122(47), 26777-26789

[2] Eaves, S. G., Hart, S. J., Whitwood, A. C., Yufit, D. S., Low, P. J. & Lynam, J. M. Chem. Commun.,

2015, 51(45), 9362-9365



Simple Metalation of Terminal Acetylenes: Synthesis of

High Purity Metal Acetylide Half- Sandwich Complexes

Daniel P. Harrison, Paul J. Low*

School of Molecular Science, University of Western Australia

Metal acetylide half-sandwich complexes are used as model complexes for

explorations of through molecule electron-transfer processes. Studies of mixed

valence systems using spectro-electrochemistry improves knowledge of electron-

transfer processes towards molecular electronic applications. Here we report a

revised, “one pot”, synthesis that affords these complexes in high-yield and excellent

purity, with minimal purification and workup required.

Examples of the electrochemical response of these compounds will be presented, and

the subtle differences in electronic structure evinced by UV-vis-NIR and IR

spectroelectrochemical studies will be discussed.



Bismuth(III) phosphinate 1D-coordination polymers as

antibacterial additives

Megan Herdman, Melissa Werrett, Rajini Brammananth, Warren Batchelor, Phil

Andrews*


Antimicrobial resistance has been recognized by the World Health Organization as a

global threat requiring urgent action.[1] The major concern of multi-resistant bacteria is

the high prevalence in hospitals and other healthcare environments. A method to

reduce the growth of bacteria on surfaces is to introduce antimicrobial functionality into

a range of surfaces within hospitals and healthcare facilities.

Bismuth has been used medicinally due to its reported antimicrobial activity and low

toxicity.[2-4] We have previously shown bismuth(III) phosphinate complexes BiPhL2

display antibacterial activity while BiL3 complexes do not inhibit bacterial growth.[5] We

have therefore synthesised a series of bismuth(III) phosphinate complexes of the type

BiPh2L to further explore the structure activity relationship. The complexes (BiPh2L)

form 1D coordination polymers (Figure 1) and thus are relatively insoluble in common

solvents, making them ideal candidates to incorporate into materials.

Antibacterial testing was conducted on the solid complexes, with the results showing

antibacterial activity towards both Gram positive and Gram negative bacteria.

Incorporation within a cellulosic polymer matrix produced Bi-containing paper, which

also showed antibacterial activity at low complex loadings. Studies into the leaching

of the complex from the composites have shown that Bi can be detected in the water,

suggesting the complex leaches out and gives rise to the zones of inhibition in

antibacterial testing.

Figure 1 – Crystal structure showing 1D-coordination polymer of the complex [BiPh2(OOP(CH3)2)].

References

[1] World Health Organization, 2014, 1-232.

[2] M.T. Busse, Iman, P. Junk. R. Ferrero, P. Andrews, Chem. Eur. J. 2013, 19, 5264-5275.

[3] A. Pathak, V. Blair, R. Ferrero, M. Mehring, P. Andrews, Chem. Commun. 2014, 50, 15232-15234.

[4] T. Kotani, D. Nagai, K. Asahi, H. Suzuki, F. Yamao, N. Kataoka, T. Yagura, Antimicrob Agents

Chemother. 2005, 50, 2729-2734.

[5] M. Werrett, M. Herdman, R. Brammananth, U. Garusinghe, W. Batchelor, P. Crellin, R. Coppel, P. Andrews.

Chem. Eur. J. 2018, 24, 12938-12949.



Applications of Gold Cocatalysis & New Phosphine

Ligands for Palladium-Catalysed Cross-Couplings

Curtis C. Ho*

*School of Natural Sciences – Chemistry, University of Tasmania

We have demonstrated a novel method employing gold(I) cocatalysis for enhancing

the efficiency of fundamental cross-coupling reactions catalysed by

palladium/phosphine complexes. Our results are consistent with cationic gold(I)

species serving primarily as phosphine scavengers generating putative

monophosphine-ligated Pd(0) active catalyst species in situ, as recently predicted by

density functional theory.[1] We will also present our progress towards developing new

classes of phosphine ligands for the generation of stable monophosphine-ligated

Pd(0) catalysts.

Figure 1. Cationic gold(I) species serving as a phosphine scavenger enhancing reactivity in cross-

couplings.

References

[1] Y. Khaledifard, B. Nsiri, S. A. Javidy, A. V. Sereshk, B. F. Yates, A. Ariafard, Organometallics 2017, 36,

2014.



Confirmation of Redox Transmetallation/Protolysis

Reaction Between HgC6F5, lanthanoid metals and protic

agents

Ryan Huo, Yu Qing Tan, Zhifang Guo, Victoria Blair, Glen B. Deacon*

School of chemistry, Monash University, Clayton 3800, Australia.

Previous studies have proposed that the redox transmetallation/protolysis (RTP)

synthesis of reactive trivalent lanthanoid organometallics, organicamides, arylamides

etc from free lanthanoid metals, HgAr2 and a protic agents (amine, formamidine,

pyrazole, phenol etc) proceeds by the following steps.1-4

To confirm this hypothesis, Hg(C6F5)2 was reacted with protic agents under one week

of sonication in dry THF. This resulted in the formation of minimal quantities of C6F5H,

suggesting that protolysis/redox transmetallation reaction (PRT) occurs at a slow rate.

An RTP reaction involving ytterbium metal, Hg(C6F5)2 and a bulky proligand (N,N’-

bis(2,6-diisopropylphenyl)formamidine (DippFormH)) in THF, proceeds to completion

in less than two hours via stirring, these combined results indicate that the RTP

reaction is favourable over protolysis/redox transmetallation PRT.

References 1. M. L. Cole , G. B. Deacon , C. M. Forsyth , P. C. Junk , K. Konstas and J. Wang , Chem. Eur. J., 2007, 13 ,

8092 -8110.

2. G. B. Deacon , G. D. Fallon , C. M. Forsyth , S. C. Harris , P. C. Junk , B. W. Skelton and A. H. White ,

Dalton Trans., 2006, 6, 802-812.

3. G. B. Deacon , C. M. Forsyth and S. Nickel , J. Organomet. Chem., 2002, 647 , 50

4. J. Lefèvre, G. B. Deacon, P. J. Junk and L. Maron, Chem. Commun., 2015, 51, 15173-15175.



Synthesis of New, Super Bulky β-Diketiminate Ligands and

their Application in Low-Oxidation State Metal Chemistry

Dafydd D. L. Jones, Cameron Jones*


β-Diketiminate (or Nacnac) ligands have found great success in coordination

chemistry since 1968.[1] The facile synthesis of these ligands has given immense

scope in tuning the sterics and electronics of these systems.[2] In particular the use of

sterically bulky Nacnac systems with large N-substituents have led to many

breakthroughs in low-oxidation state metal chemistry, with Nacnac systems using 2,6-

diisopropyl (Dipp) aniline being most famous. More sterically demanding Nacnac

systems have proven to be problematic as they either are synthetically difficult to

access or can undergo decomposition reactions due to proximal acidic protons.

Recent reports have shown that replacing the isopropyl groups of the Dipp aniline with

isopentyl groups (DiPeP), has shown promise with the synthesis of reactive group two

hydrides and a low-oxidation magnesium (I) dimer, which is of particular note due to

its large Mg-Mg bond distance compared to its analogues.[3,4] This does still require

several synthetic steps to the DiPeP aniline, and some of these complexes are difficult

to isolate due to their high solubility.

Therefore the synthesis of bulkier, but more synthetically accessible anilines was

herein explored. The aim of which is to synthesise new β-diketiminate ligands, and to

explore the utility of these ligands in low-oxidation state metal chemistry, particularly

that of magnesium and aluminium (Figure 1). The successful synthesis and

stabilisation of magnesium complexes is discussed, as well as comparative reactivity

and steric bulk compared to the established analogues.

Figure 1. A super bulky Nacnac ligand system using 2,4,6-tricyclohexyl aniline, with the synthetic route

to one of the target metal complexes, a magnesium (I) dimer.

References

[1] Parks, J. E, Holm, R. H. Inorg. Chem. 1968, 7, 1408-1416

[2] C. Chen, S. M. Bellows, P. L. Holland, Dalton Trans., 2015, 44, 16654-16670

[3] T. X. Gentner, B. Rösch, G. Ballmann, J. Langer, H. Elsen and S. Harder, Angew. Chem., Int. Ed.,

2019, 58, 607–611.

[4] B. Rösch, T. X. Gentner, H. Elsen, C. A. Fischer, J. Langer, M. Wiesinger, S. Harder, Angew.

Chem., Int. Ed., 2019, 58, 5396–5401.



Diferrocenyl Co- and Fe-Carbonyl Clusters

Marcus Korb,a* Sebastian Walz,b Xianming Liu,b Marco Rosenkranz,c Alex Popov,c

and Heinrich Langb

a School of Molecular Sciences, The University of Western Australia, Perth; b Inorganic

Chemistry, TU Chemnitz; c Institute for Solid State Research, Dresden, Germany

The introduction of ferrocenyl fragments as redox active moieties allows for the study

of electronic and Coulombic interactions through the core of various types of

molecules. Iron- and Cobalt-based clusters were intensively been studied in the 1970s

and recently returned to focus with demonstrations of interactions with the iron atom

of an attached ferrocenyl moiety in a monomeric model compound.[1] Although,

replacement of carbonyls by e.g. dppf is a common procedure to attach ferrocenyl

groups to cluster cores, direct functionalization is less readily achieved.

Applying a recently published procedure for the synthesis of pure FcPCl2,[2] we

synthesized novel derivatives of well-known cluster species Fe3(CO)9(μ3-PFc)2 (1) and

Co4(CO)10(μ3-PFc)2 clusters (2) (Figure 1). The electrochemical behaviour was

investigated for the anodic (ferrocenyl-based) and cathodic (core-based) region,

revealing stable one-electron redox products, which were further explored by in situ

NIR and IR spectroelectrochemical measurements. Furthermore, the presence of the

phosphorous atoms allowed for detailed in situ EPR results of 1∙– and confirmed a

core-rearrangement at low potentials.

Figure 1. ORTEP (left, 50 % probability level) and CV and Square Wave diagrams (right) of 1. (Fc* =

Decamethylferrocene.)

References

[1] F. Döttinger, M. R. Ringenberg, Organometallics 2019, 38, 586–592; M. Häßner, J. Fiedler, M. R.

Ringenberg, Inorg. Chem. 2019, 58, 1742–1745. [2] B. A. Surgenor, L. J. Taylor, A. Nordheider, A. M.

Z. Slawin, K. S. Athukorala Arachchige, J. D. Woollins, P. Kilian, RSC Adv. 2016, 6, 5973–5976.



Synthesis and Spectroelectrochemical Studies of

Ruthenium Alkynyl Complexes

George A. Laffan,1 Mark G. Humphrey,1 Mahbod Morshedi1

1Research School of Chemistry, Australian National University, Canberra, ACT, 2601

Extended ruthenium alkynyl complexes have been synthesized, and the possibility of

switching their molecular optical properties via electrochemical means has been

investigated. Incorporation of inductive electron-donating or – withdrawing

substituents (NO2 and NPh2 respectively) at the meta-position of the arylalkynyl ligand

bridges, as shown below, modifies the electronic characteristics of the complexes. The

target complexes were designed to permit sequential and reversible oxidation of the

complexes through two oxidation states. Each oxidation step induced a noticeably

unique optical response, creating multistate molecular switches.



The odd nature of tungsten C3 and C5 complexes

Richard A. Manzano, Anthony F. Hill

Research School of Chemistry, Building 137, Sullivans Creek Road, The Australian

National University, Canberra, ACT, 2601, Australia.

Transition metal based polyyne chemistry has been an emerging topic within the

organometallics field. In particular, the development of odd-numbered sp-hybridised

carbon chains have seen a recent surge within the literature over the past decade.[1]

A simple, yet elegant method has been developed towards the synthesis of tungsten

propargylidynes [W(CCCR)(CO)2Tp*] (C3)[2] and pentadiynylidyne

[W(CCCCCR)(CO)2Tp*] (C5)[3] complexes via palladium-mediated cross coupling

of the tungsten bromocarbyne [W(CBr)(CO)2Tp*] and various species of terminal

alkynes.

Further reactivity of the trimethylsilylpentadiynylidyne [W(CCCCCSiMe3)(CO)2Tp*]

demonstrates its utility as a C5 scaffold to afford pentacarbido complexes.

Crystal structure of the trimethylsilylpentadiynylidyne complex [W(CCCCCSiMe3)(CO)2Tp*)]

References

[1] Hill, A. F.; Colebatch, A. L.; Cordiner, R. L.; Dewhurst, R. D.; McQueen, C. A. M.; Nguyen, K. T. H.

D.; Shang, R.; Willis, A. C. Comments on Inorganic Chemistry 2010, 31, 121-129.

[2] Hill, A. F.; Manzano, R. A. Dalton Transactions 2019, 48, 6596-6610.

[3] Hill, A. F.; Manzano, R. A. Angewandte Chemie International Edition 2019, 58, 7357-7360.



Towards the Assembly Triple Hydrogen Bonded Transition

Metal Complexes

Aidan P. McKay, David A. McMorran*


The understanding of the structural features within molecular compounds that facilitate

their intermolecular assembly by hydrogen bonding, either with themselves or with

complementary species, is important for the construction of functional co-crystallised

systems and the development of rational methods for their synthesis.[1, 2] Here we will

describe a range of transition metal complexes containing known and novel ligands

which contain either the acceptor-donor-acceptor (ADA) or the complementary donor-

acceptor-donor (DAD) motifs, and our recent results in characterising these in the solid

state. Structures of palladium(II) and platinum(II) 2-phenylpyridine, ruthenium(II) bis-

bipyridine and iridium(III) bis-phenylpyridine complexes with 1,5-diarylbiguanides,

orotic acid, pyridylmethylenehydantion, and diaminotriazine-pyridyltriazole ligands are

presented, along with our progress towards obtaining complex-complex co-crystals.[3,

4]

Figure.1. X-ray crystal structure of palladium(II) phenylpyridine diarylbiguanide co-crystallised with the

complementary organic molecule dimethylaminonaphthalimide.

[1] S. Bhattacharya, K. S. Peraka and M. J. Zaworotko, in Co-crystals: Preparation, Characterization

and Applications, The Royal Society of Chemistry, London, United Kingdom, 2018

[2] G. R. Desiraju, J. J. Vittal and A. Ramanan, Crystal Engineering, Co-Published with Indian Institute

of Science (IISc), Bangalore, India, 2011.

[3] A. P. McKay, G. E. Shillito, K. C. Gordon and D. A. McMorran, CrystEngComm, 2017, 19, 7095-

7111

[4] A. P. McKay, J. I. Mapley, K. C. Gordon, D. A. McMorran, Chem. Asian J. 2019, 14 (8), 1194-1203.



A Dipolar Molecular Switch for Nonlinear Optics

Mahbod Morshedi, Katy A. Green, Marie P. Cifuentes, Mark G. Humphrey*

Research School of Chemistry, Australian National University, ACT 2601, Australia

Email: [email protected]

Designing and creating multistate switches that respond to different stimuli (light,

chemicals, etc.) is a current challenge in the push to replace silicon-based logic gates

and other computational components. The applications can potentially be even more

diverse if switching exploits not only the linear properties of light but also the nonlinear

properties. The dipolar dithienylperfluorocyclopentene (DTE) unit has been

conjugated with electrochemical and chemical switching modules to produce

centrosymmetric molecules with a large number of switchable nonlinear optical

states.[1] Extensions of this research to dipolar examples will be described.

Six states of the dipolar Ru-DTE switch.

References

[1] K. A. Green, M. P. Cifuentes, T. C. Corkery, M. Samoc, M. G. Humphrey, Angewandte Chemie International Edition 2009, 48, 7867-7870.



Synthesis and characterization of bismuth (III)

phosphonates as antimicrobial polymeric materials

Shazia Nawaz, Liam Stephens, Kei Saito, Phil Andrews*


Microbes are threatening human safety and well-being resulting in a number of

infectious diseases.1 This is an alarming situation because a resistant infection can

cause deaths, can spread to others imposing a lot of costs to society as well as

individuals. Three hundred million premature deaths are estimated by 2050 to be

caused by antibiotic resistance if the problem is not addressed properly.2

The compounds of Bismuth (III) have been used for the treatment of skin conditions,

gastrointestinal infections and disorders.3 We have synthesized bismuth (III)

phosphonate complex BiPhL that is insoluble in common solvents. The complex

exhibits antibacterial activity in the solid state towards Staphylococcus aureus (S.

aureus), Methicillin-resistant Staphylococcus aureus (MRSA), Acinetobacter

baumannii (A. baumannii) and Pseudomonas aeruginosa (P. aeruginosa).

Figure 1- General synthetic route of bismuth (III) vinyl phosphonate formation

Antimicrobial polymers are of considerable attention both in industrial and academic

research. Vinyl phosphonic acid was polymerised using different azo initiators and the

resultant polymer reacted with triphenyl bismuth. Polymer itself and polymeric bismuth

compounds also display antibacterial activity against both Gram positive and Gram

negative bacteria. Polymeric bismuth compound is also insoluble in common solvents.

These compounds have been characterised using Gel permeation chromatography

(GPC), solid state NMR spectroscopy, IR and elemental analysis.

References

(1) Huang, K.-S.; Yang, C.-H.; Huang, S.-L.; Chen, C.-Y.; Lu, Y.-Y.; Lin, Y.-S. Recent Advances in

Antimicrobial Polymers: A Mini-Review. Int. J. Mol. Sci. 2016, 17 (9).

(2) WHO | Antimicrobial Resistance. WHO 2018. (3) Paladini, F.; Pollini, M.; Sannino, A.; Ambrosio, L. Metal-Based Antibacterial Substrates for

Biomedical Applications.



A one-pot route to thioamides and Amidines discovered by

fundamental gas-phase studies

Asif Noor1, Yang Yang1, J. Li1, G. N. Khairallah1, Z Li1, H Ghari2, A. J. Canty3, A. Ariafard2*, P. S. Donnelly1* and R. A. J. O’Hair1*

1School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, Melbourne, Victoria 3010, Australia.

2Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University, Shahrak Gharb, Tehran, Iran.

3School of Physical Sciences, University of Tasmania, Hobart, Tasmania 7001, Australia

Thioamides and amidines are useful compounds for applications in organic synthesis

and medicinal chemistry. A simple “one pot” palladium mediated synthesis of

thioamides and amidines from aromatic carboxylic acids (Figure 1) will be presented.

The methodology was developed using a combination of gas-phase multi-stage mass

spectrometry experiments and DFT calculations. The gas phase chemistry was

extended to the condensed phase, where the individual steps were examined via 1H

NMR spectroscopy before optimising the “one pot” method. A total of eight thioamides

and six amidines were synthesized and fully characterized, including via X-ray

crystallography.

This new chemistry takes advantage of the isoelectronic analogy to open up a new

class of reactions, coined CO2ExIn (ExIn = Extrusion-Insertion) that could be broadly

applicable to other substrates. These results highlight the emergence of fundamental

gas-phase studies to direct the discovery of new reactions for use in organic synthesis.

Figure 1 Palladium catalysed decarboxylative transformation of aromatic carboxylic acids into

thioamides



A New Approach to Design MOF Based Catalysts

R. A. J. O’Hair*,[b] A. Mravak, [b] M. Krstić [b] and V. Bonačić-Koutecky*[b]

[a] School of Chemistry, The University of Melbourne, Australia

[b] Center of Excellence for Science and Technology, University of Split, Croatia.

We have been using mass spectrometry (MS) based methods and DFT calculations

to design transition metal catalysts from the ground up for the selective

decarboxylation of formic acid,[1] a reaction of considerable interest for hydrogen

storage applications and in situ generation of H2. Here we describe a new conceptual

approach for the design of a heterogeneous metal-organic framework (MOF) catalyst

based on UiO-67 for the decomposition of formic acid. Models for the {CuH} reactive

catalytic site at the organic linker are assessed. In the first model system, MS

experiments and DFT calculations on a fixed charge bathophen ligated copper hydride

complex, [(phen*)Cu(H)]2-, were used to demonstrate that it selectively decomposes

formic acid into H2 and CO2 via a two step catalytic cycle. In the first step liberation of

H2 to form the carboxylate complex, [(phen*)Cu(O2CH)]2- occurs, which in the second

step selectively decomposes via CO2 extrusion to regenerate the hydride complex.

DFT calculations on four other model systems showed that changing the catalyst to

neutral [(LCu(H)] complexes or embedding it within a MOF results in mechanisms

which are essentially identical. Thus catalytic active sites located on the organic linker

of a MOF appear to be close to a gas-phase environment, thereby benefitting from the

favorable characteristics of gas-phase reactions and validating the use of gas-phase

models to design new MOF based catalysts.

References

[1] A. Zavras, et al., Nat. Commun. 2016, 7, 11746; A. Zavras, et al., Dalton Trans. 2016, 45, 19408; A.

Zavras, et al., ChemCatChem 2017, 9, 1298; M. Krstić, et al., ChemCatChem 2018, 10, 1173.

[2] R.A.J. O’Hair, et al., ChemCatChem 2019, 11, 2443–2448.



Selenium functionalised metal-carbon chains –

Alkynylselenolatoalkylidynes (LnMC–Se–CCR)

Chee S. Onn, Benjamin J. Frogley, Anthony F. Hill*

Research School of Chemistry, Australian National University.

The reactions of [W(≡CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-

yl)borate) with lithium alkynylselenolates LiSeC≡CR (R = SiMe3, SiiPr3, nBu, tBu, Ph,

p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(≡CSeC≡CR)(CO)2(Tp*)].

Desilylation of the SiMe3 complex furnishes the parent [W(≡CSeC≡CH)(CO)2(Tp*)],

which may be further derivatised by deprotonation and treatment with

triphenylcarbenium or triphenyltetrel chlorides to give mixed-heteroatom products

[W(≡CSeC≡CEPh3)(CO)2(Tp*)] (E = C, Si, Ge, Sn, Pb).

This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes

[(Tp*)(CO)2W≡CSeC≡CSiRR′C≡CSeC≡W(CO)2(Tp*)] (R, R′ = Ph, CH3) are obtained,

bridged by unsaturated units interrupted by two different main-group heteroatoms.

Finally, the trimetallic analogues, [{(Tp*)(CO)2W(≡CSeC≡C)}3SiR] (R = Ph, Et), may

be prepared in the same manner from appropriate organotrichlorosilanes.

Professor Dr Anthony F. Hill

RESEARCH SCHOOL OF CHEMISTRY, BUILDING NO. 137 T: +61 2 6125 8577 AUSTRALIAN NATIONAL UNIVERSITY E: [email protected]

CANBERRA ACT 0200 AUSTRALIA http://chemistry.anu.edu.au

CRICOS Provider No. 00120C

April 9th 2019 To the Editors

Dalton Transactions

We would appreciate your consideration of the accompanying manuscript for publication as a

full paper in Dalton Transactions.

Some years ago we described the (only) alkynylselenolatocarbyne complexes

[Mo(≡CSeC≡CR)(CO)2(Tp*)] (R = CMe3, SiMe3, p-tolyl) which feature both Mo≡C and C≡C triple

bond bound to a selenoether linkage. Perhaps not surprisingly, the Mo≡CSeC≡C- linkage offers a

number of functionalities capable of undergoing unusual transformations. In the current paper we not

only extend this chemistry to the first tungsten derivatives (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl)

but also investigate the possibility of constructing more elaborate bi- an tri-nuclear examples that

emerge from functionalisation of the parent complex [W(≡CSeC≡CH)(CO)2(Tp*)] which is in turn

accessible via desilylation of the SiMe3 derivative. Deprotonation of the parent allows access to

[W(≡CSeC≡CLi)(CO)2(Tp*)] (in situ) which undergoes nucleophilic substitution with a range of

group 14 electrophiles to afford inter alia the entire tetrel substituted series

[W(≡CSeC≡CAPh3)(CO)2(Tp*)] (A = C, Si, Ge, Sn, Pb) and polynuclear silanes

R2Si{C≡W(CO)2(Tp*)}2 and RSi{C≡W(CO)2(Tp*)}3 (R = Me, Et, Ph).

We expect that the work will interest those in the filds of carbyne chemistry, carbon-wire

chemistry, structural chmistry and the interface of transition and main-group metal chemistries.

Yours faithfully,

Anthony F. Hill

Page 2 of 71Dalton Transactions



Electron transfer processes and mixed-valence chemistry: studies with metal complexes featuring carbon-rich

ligands Parvin Safari,a Simon Gückel,b Josef Gluyas,a Martin Kaupp,b Paul J. Lowa*

a School of Molecular Sciences, The University of Western Australia

b Institut fur Chemie, Technische Univesität Berlin

Electron transfer is a ubiquitous process in chemistry, and the exchange of an electron

between two sites might be considered the most elementary of all chemical reactions.

Mixed-valence (MV) complexes {LxMn}{-bridge}(M(n+1)Lx} in which two redox centres

{MLn}, identical in every way except their formal oxidation state, are linked by a

bridging ligand have served as powerful model systems through which to study the

fundamentals of the intramolecular electron exchange reaction.

General scheme for complexes containing carbon rich bridges

In turn, a deeper understanding of the electronic structure and charge distribution in

these systems has allowed the development of a range of molecular optoelectronic

materials. Conventionally, the electronic character of a MV complex and degree of

‘electronic coupling’ between the redox sites through the bridge is determined using

the relationships developed by Hush and described within the general framework of

Marcus-Hush theory.

However, whilst appealing, the analysis of MV compounds using the Hush model is

non-trivial in many cases, with the critical IVCT band often overlapped with other

electronic transitions and, in the case of strongly coupled / highly delocalised systems,

asymetrically shaped. Furthermore, these analyses are typically based on the

assumption that the MV complex can be adequately described by one single, dominant

molecular conformation while MV complexes are often present as a complex

conformational mixture, with member differing by the relative orientation of the metal

end-caps around the M-bridge-M’ axis. As electronic structure depends on orbital

overlap along the M-bridge-M molecular backbone, these conformational factors can

play a significant role in the description of the electronic structure of the compound in

solution.

In this poster, we will represent a range of carbon-rich bridged bi- and multi-metallic

complexes that are designed to carry spectroscopic probes to permit the development

of new strategies for the experimentally convenient study of electron transfer

processes.



Reactivity of Newly Discovered Trans-Difluorogold(III)

Complexes

Lachlan T. Sharp-Bucknall, Dr. Jason Dutton*

School of Molecular Sciences, La Trobe University

Development of new gold fluoride species is of interest because of their rarity and

potential to catalytically generate fluorinated molecules.

Our group has recently produced a group of trans difluorogold(III) complexes that are

supported by N-ligands. These complexes are stable, easily isolable and are the first

examples of trans gold difluorides supported by N-ligands. [1]

Due to the general rarity and relative novelty of these complexes, their reactivities are

yet to be substantially investigated. Consequentially, this work seeks to cover these

investigations by following the reactivities of our complexes with various substituents

such as carbenes, alkynes and trimethylsilyl functionalised species.

References

[1] M. Albayer, R. Corbo and J. L. Dutton, Chem. Commun., 2018, 54(50), 6832



Experimental and Theoretical Properties of Low-Oxidation

State Aluminium Amidinate Complexes

Cory D. Smith, Cameron Jones*


The chemistry of aluminium in the +1 oxidation state is vastly unexplored, with only

two neutral monomeric species having been fully characterised.[1-2] The most widely

used of these is a (NacNac)Al: (NacNac = β-diketiminiate) species synthesised by

Roesky in 2003. This compound has been shown by various groups to oxidatively add

a range of σ- and π-bonds.[3] Additionally, Aldridge and Goicoechea recently reported

the synthesis of an aluminium(I) anion, formed through reduction of an aluminium

iodide species bearing a NON pincer ligand.[4]

Current work within the Jones group is aimed at producing Al(I) species bearing

amidinate backbones containing bulky motifs, which have previously been shown to

stabilise the first known dimeric strontium hydride species, for example.[5] Additionally,

the use of a bulky aliphatic amine will hopefully enable the amidinate to better stabilise

a low-oxidation state aluminium centre.

[1] Cui, C.; Roesky, H. W.; Schmidt, H.-G.; Noltemeyer, M.; Hao, H.; Cimpoesu, F. Angew. Chemie 2000, 39 (23), 4274–4276. [2] Xiaofei Li; Xiaoyan Cheng; Haibin Song, and; Cui*, C. Organometallics 2007, 26, 1039-1043 [3] Chu, T.; Korobkov, I.; Nikonov, G. I. J. Am. Chem. Soc. 2014, 136 (25), 9195–9202.

[4]Hicks, J.; Vasko, P.; Goicoechea, J. M.; Aldridge, S. Nature 2018, 557 (7703), 92–95.

[5] de Bruin-Dickason, C. N.; Sutcliffe, T.; Alvarez Lamsfus, C.; Deacon, G. B.; Maron, L.; Jones, C.

Chem. Commun. 2018, 54 (7), 786–789.



Superphenylphosphines: Nanographene-based Ligands

that Direct Coordination and Bulk Assembly

Jordan N. Smith,1,2 James M. Hook,3 Nigel T. Lucas*1,2

1Department of Chemistry, University of Otago, Dunedin, New Zealand 2MacDiarmid Institute for Advanced Materials and Nanotechnology, New Zealand

3Mark Wainwright Analytical Centre, University of NSW, Sydney, Australia

Phosphines are ubiquitous throughout coordination and organometallic chemistry, and

are common supporting ligands in transition metal catalysis. An attraction of tertiary

phosphines is the ability to tune their electronic and steric properties. While

trialkylphosphines are some of the most electron-donating examples, aryl phosphines

tend to be more easily handled and are sufficiently strong donors for many

applications. Furthermore, phenyl/aryl groups on phosphine ligands in metal

complexes can play a major role in the driving the supramolecular order.1

Large polycyclic aromatic hydrocarbons have gained considerable interest because of

their electronic and optical properties, and the strong π-interactions that direct their

assembly into columnar stacks.2 One such nanographene is hexa-peri-

hexabenzocoronene (HBC), consisting of 42 carbon atoms in 13 fused rings; the

hexagonal geometry and stability comparable to benzene has led to HBC being

described as ‘superbenzene’ (Fig. 1). As part of our research into nanographene-

based ligands, we have synthesized a series of ‘superphenylphosphines’.3 The

coordination of these phosphines to several different metals has been investigated,

along with the role the HBC fragment plays on coordination geometry and driving

assembly in the crystalline phase.

Figure 1. Diagrams of superbenzene, superphenylphosphines 1 and 3, and the crystallographically-

determined structure of the complex PdCl2(1)2.

References

[1] I. Dance, M. Scudder, CrystEngComm, 2009, 11, 2233.

[2] K. Müllen, ACS Nano., 2014, 8, 6531.

[3] J. N. Smith, J. M. Hook and N. T. Lucas, J. Am. Chem. Soc, 2018, 140, 1131.



Selective Activation of Alkynes through Cumulene

Intermediates

Rachel R. Steen a,b, Michael Hall b, Jason Lynam a*, Paul Low b*

a Department of Chemistry, University of York, UK, b School of Molecular Science,

University of Western Australia

Transition metal complexes are important in the synthesis of various pharmaceutical

and agrochemical products and can be used to facilitate the formation of new C-C and

C-heteroatom bonds. Cumulenes, chains of sp-hybridised carbon atoms, terminated

by an sp2-hybridised carbon atom and often a metal ligand fragment, are of particular

interest due to their unique reactivity; electrophilic attack is more likely to occur at even

numbered carbons and nucleophilic attack at the odd1. However they are difficult to

synthesise once the chain length extends beyond 4 atoms.

Previous work2 suggested that aromatic spacer groups may be used to stabilise a

cumulene chain, and DFT studies showed a cumulenic intermediate in the reaction of

the vinylidene trans-[Ru(=C=CHC6H4-4-C≡CH)Cl(dppm)2]BF4 and [NnBu4]Cl. Here, a

quinoidal cumulene has been stabilised in the coordination sphere of a ruthenium and

trapped through reaction with nucleophiles at the seventh carbon.

References

1 C. Bruneau and P. Dixneuf, Eds., Metal Vinylidenes and Allenylidenes in Catalysis, Wiley‐

VCH, Weinheim, Germany, 2008.

2 S. G. Eaves, S. J. Hart, A. C. Whitwood, D. S. Yufit, P. J. Low and J. M. Lynam, Chem.

Commun., 2015, 51, 9362–5.



Synthesis of Novel Bismuth Tetrazole Thiolate Complexes

as Potential Antimicrobials

Liam J. Stephens, Tom H. Moran, Rebekah N. Duffin, Melissa V. Werrett, Phil C.

Andrews*


Antibiotic resistant bacteria are becoming increasingly common. New resistance

mechanisms are continually being discovered, with new genes and vectors for

transmission of resistance identified on a regular basis.[1] This inexorable rise of

bacterial resistance has been further intensified by the lack of new antibiotics being

developed over the last 20 years. Organometallic Bismuth (Bi) compounds offer an

attractive alternative to the typically used organic molecules in combating antibiotic

resistance, due in large to their limited toxicity against human cells (as demonstrated

by pepto-bismol used to treat gastrointestinal infections).

Since their discovery in 1885, the tetrazole moiety has been identified as a key

functionality in a host of clinically used pharmaceuticals including anti-inflammatory,

antifungal, anticancer and antibiotics.[2] With this knowledge in mind, we explored the

possibility of developing tetrazole containing Bi complexes and have since

synthesised, and fully characterised, 18 new derivatives of this kind. A number of these

novel compounds have demonstrated excellent antibiotic activity against a broad

spectrum (Gram positive and Gram negative) of bacteria. Further biological assays

will be discussed including time-kill assays, which revealed the bacteriostatic nature

of these novel compounds.

Figure 1: The novel Bismuth tetrazole thiolate complexes that have been synthesised and tested

against a broad spectrum of bacteria.

References

[1] J. M. A Blair, L. J. V Piddock, Molecular Mechanisms of Antibiotic Resistance. Nature Reviews

Microbiology, 13, 42-51, (2015).

[2] V. A. Ostrovskii, R. E. Trifonov, Developments in Tetrazole Chemistry 2009-16. Advances in

Heterocyclic Chemistry, 123, 1-62, 2017.



Biological Studies of a Molybdenum based Cyanide Poisoning Antidote

Sigridur G. Suman1*, Linda A. Hancock1, Johanna M. Gretarsdottir1, Stefan Sturup2, Ian H. Lambert3

1Science Institute, University of Iceland, Dunhagi 3, 107 Reykjavik, Iceland.

2University of Copenhagen, Department of Pharmacy, Universitetsparken 2, 2100 Copenhagen Ø, Denmark.

3University of Copenhagen, Department of Biology, Universitetsparken 13, 2100 Copenhagen Ø, Denmark

Cyanide poisoning antidotes function to prevent cyanide from permanently inhibit cytochrome c oxidase who is primary lethal target [1]. Although these antidotes are efficacious, their donwsides prevent their use for emergency treatment of cyanide poisoning [2]. Since cyanide is an endogenous molecule [3], a physiological mechanism to transform cyanide into a non-toxic thiocyanate involves the rhodanase enzyme [4].

Molybdenum sulfur complex salts are capable of converting cyanide to thiocyanate [5]. Selected compounds were evaluated for cytotoxicity in three different cancer cell lines [6]. The compounds proved to have low cytotoxicity compared to cisplatin and even less so for alkali salts compared to tetraalkylammonium salts. Uptake and distribution in cells showed the compounds enter the cells and distribution was confirmed in cytosol, nucleus and mitochondria [5]. Toxicity in vivo was studied in a mouse model showing the compounds are relatively safe [7]. Pharmacokinetic data revealed a selected compound enters the bloodstream rapidly and exits in a timely manner [7]. Inhalation study in a mouse model showed modest efficacy against a challenge [7]. The presentation will summarize these findings and discuss their relevance for an emergency antidote to treat cyanide poisoning.

Financial support by the Icelandic Technology Development Fund (Rannís Tækniþróunarsjóður) grant nr. 164784 and by The Icelandic Centre of Research grant nr 140945 is gratefully acknowledged.

References

[1] H. B. Leavesley, L. Li, K. Prabhakaran, J. L. Borowitz, and G. E. Isom, “Interaction of Cyanide and Nitric Oxide with Cytochrome c Oxidase: Implications for Acute Cyanide Toxicity”. Toxicological Sciences 2008, 101(1), pp. 101-111.

[2] S. G. Suman, J. M. Gretarsdottir, “Chemical and Clinical Aspects of Metal Containing Antidotes for Poisoning by Cyanide”, Met. Ions Life Sci., Eds. A. Sigel, E. Freisinger, R. K. O. Sigel, Walter de Gruyter GmbH, Berlin, Germany, 2019, (19), pp. 359-391.

[3] P. G. Gunasekar, J. L. Borowitz, J. J. Turek, D. A. V. Horn, G. E. Isom, “Endogenous Generation of Cyanide in Neuronal Tissue: involvement of a Peroxidase System”. J. Neurosci. Res. 2000, 61, pp. 570-575.

[4] K. R. Leininger, J. W., The Mechanism of the Rhodanese-catalyzed Thiosulfate Cyanide Reaction. J. Biol. Chem. 1967, 243 (April 25), pp. 1892-1899.

[5] J. M. Gretarsdottir, “Syntheses of new molybdenum-sulfur complexes: Catalytic transformation of cyanide to thiocyanate and in vitro biological studies“, PhD Thesis, University of Iceland, 2018.

[6] Gretarsdóttir, J. M, Bobersky, S., Metzler-Nolte, N., Suman, S. G., “Cytotoxicity Studies of Water Soluble Coordination Compounds with a [Mo2O2S2]2+ Core” J. Inorg. Biochem. 2016, 160, pp. 166-171.

[7] L. A. Hancock, “In vivo Analyses of a Mo2O2S4-Based Metallodrug”, MS Thesis, University of Iceland, 2018.



A new rotational isomer of bis(pentafluorophenyl)mercury

[Hg(C6F5)2]

Yu Qing Tan, Niko T. Flosbach, Céline Leonhardt, Glen B. Deacon*, Victoria Blair,

Peter C. Junk


College of Science and Engineering, James Cook University, Townsville 4811, Qld,

Australia.

It has been found that bis(pentafluorophenyl)mercury, possesses a previously

unknown second rotational isomer. Both rotamers yield identical IR and NMR spectra

and distinction between them can only be ascertained from their X-ray structures and

microscopic imaging (Figure 1).

X-ray structure (reported rotamer): orthorhombic, space group P212121, a =5.762(1),

b=10.645(1), c= 20.296(2) Å.1 Rotational angle of the arene rings: 58.03°.

X-ray structure (new rotamer): monoclinic, space group P21/n, a= 11.7060(3), b=

7.8531(2), c= 13.5429(4) Å. Rotational angle of the arene rings: 74.62°.

Figure 1: Side by side comparison of reported Hg(C6F5)2 crystals and the new

rotational isomer of Hg(C6F5)2

The new conformer was attained from a variety of methods. Recrystallization of

Hg(C6F5)2 was done by dissolving Hg(C6F5)2 in n-hexane and heating. Upon standing

for two weeks, block-like crystals were achieved in situ.

References

1 D. L. Wilkinson, J. Reide, G. Müller, Z. Naturforsch, 1991, 46b, 285-288.



Synthesis, Characterization and Biological Activity of

Select [Pt(2-pyridyl-1,2,3-triazole)2]2+ “Click” Complexes

James E. Foote,1,2 Dan Preston,1,3 Roan Vasdev,3 Synøve Scottwell,1 Quinn van

Hilst,1,2 Greg I. Giles,3 Heather J. L Brooks,2 James D. Crowley.1,*

1 Department of Chemistry, University of Otago, Dunedin, New Zealand

2 Department of Microbiology and Immunology, University of Otago, Dunedin, New

Zealand

3 Department of Pharmacology and Toxicology, University of Otago, New Zealand

While the biological importance of platinum complexes has been demonstrated via

their use in anti-cancer therapy, platinum complexes also possess unique and

interesting activity against bacteria.[1] Recently, Crowley and co-workers reported the

synthesis of a pair of square planar pyridyl-triazole (pytri) platinum(II) complexes that

exist solely as single isomers due to interligand hydrogen bonding.[2] As these

complexes can be readily generated via the Cu(I)-catalysed azide-alkyne

cycloaddition (CuAAC) reaction with differing appending groups, they allow for the

generation of a family of complexes. Previous work in the Crowley group has shown

that the antibacterial potency of a mono-nuclear pytri system can be focused by

varying the length of the appended alkyl chain.[3] As such, we set out to synthesise a

family of square planar [Pt(pytri)2]2+ complexes with appended alkyl or aromatic

substituents and investigate their antimicrobial properties. The complexes were

characterized via 1H and 13C NMR spectroscopy, ESI-MS and elemental analysis.

Their antibacterial activity was determined against S. aureus (ATCC 25923) and E.

coli (ATCC 25922), as well as cytotoxicity data gathered for the lead complexes

against a selection of cell lines (A549 (lung cancer), MDA MB231 (breast cancer),

WM266 (human melanoma) and HDFa (normal human dermal fibroblasts)).

Preliminary mode of action studies as well as screening against a wider spectrum of

bacteria (MRSA (MR 4393 and MR 4549), M. smegmatis and A. calcoaceticus) was

performed for the lead complex identified.

Figure 1: Synthesis of platinum(II) complexes: (i) (a) NaN3, DMF/H2O (4:1), 110oC, 1 h, (b) sodium ascorbate, CuSO4, RT, 12 h; (ii) (a) [Pt(DMSO)2Cl2], AgNO3, 10 min,(b) absence of light, 85oC, 12 h.

[1] (a) Rosenberg, B.; Van Camp, L.; Krigas, T., Nature 1965, 205 (4972), 698-699; (b) Gibson, D., J. Inorg. Biochem. 2019, 191, 77-84. [2] Preston, D.; Tucker, R. A. J.; Garden, A. L.; Crowley, J. D., Inorg. Chem. 2016, 55 (17), 8928-8934. [3] Kumar, S. V.; Scottwell, S. O.; Waugh, E.; McAdam, C. J.; Hanton, L. R.; Brooks, H. J.; Crowley, J. D., Inorg. Chem. 2016, 55 (19), 9767-9777.



Catalytic activity of N-heterocyclic carbene Ag(I) amides

Daniel Van Zeil, John Kelly, Aaron Boutland, Victoria Blair*


Within the group 11 “coinage” metals, silver is often overlooked due to its instability

under ambient light and growing interest in gold analogues of established copper

catalysed reactions[1]. Silver is most often used in Lewis acid catalysis in the form of a

silver salt, however, in a recent study by Kobayashi[2] the use of copper and silver

amides as catalysts was explored with [3+2] cycloaddition reactions. With this being

the only example of silver amide catalysis in the literature, this area of chemistry is

primed for exploration

Our research group is currently exploring the synthesis and characterisation of a

library of NHC silver(I) amides and testing their catalytic activity via simple hydro-

functionalisation reactions. By changing the bulkiness, aromaticity and chirality of both

the R groups on the NHC carbene and the R’ groups on the amide, we hope to

optimise catalytic activity and improve light stability.

Figure 1: Target NHC stabilised silver(I) amide complex and candidate R groups.

References

[1] Díez-González, S. and S. P. Nolan (2008). "Copper, Silver, and Gold Complexes in Hydrosilylation

Reactions." Accounts of Chemical Research 41(2): 349-358.

[2] Yamashita, Y. and Kobayashi, S. 2013. Metal Amides as the Simplest Acid/Base Catalysts for Stereoselective Carbon–Carbon Bond‐Forming Reactions. Chemistry - A European Journal. 19, 29 (2013), 9420–9427.

R = = R’



Deep Blue Organic Light Emitting Diodes Based on N-

Heterocyclic Carbene Platinum(II) Complexes

Koushik Venkatesan*

Department of Molecular Sciences, Macquarie University, North Ryde, NSW 2109

New efficient light-emitting materials are crucial for applications in sensors,

photoelectronic devices, and optical devices. Transition metal complexes have been

employed as triplet emitters for application in phosphorescent organic light emitting

devices (PhOLEDs). [1, 2] Transition metals such as iridium and platinum with suitable

ligands allow for tailoring the photoluminescent properties. Achieving high stability,

quantum efficiency and specific chromaticity of platinum(II) complexes present a major

challenge in this field. While a large variety of green and red emitters with excellent

luminescent properties is known, the focus of the ongoing research lies on deep blue

emitting complexes. In this work, we demonstrate that deep blue PHOLEDs with high

external quantum efficiency can be achieved through a rational combination of ligands

around the platinum(II) centre.[3]

References

[1] M. A. Baldo, D. F. O’Brien, M. E. Thompson, S. R. Forrest, Phys. Rev. B 1999, 60, 14422-14428.

[2] Y. Chi, P.-T. Chou, Chem. Soc. Rev. 2010, 39, 638-655.

[3] M. Bachmann, Y. Zhang, C.-C. Wu, O. Blacque, K. Venkatesan, Manuscript under preparation.



Synthesis, Linear Optical, and Second-/Third-Order NLO

Properties of Porphyrin-Bridged Push-Pull Ruthenium

Complexes

Huan Wang, Mahbod Morshedi, Cristóbal Quintana, Mark G. Humphrey*

Research School of Chemistry, Australian National University, Canberra, ACT 2601

The synthesis of two porphyrin-bridged push-pull ruthenium complexes (13, 16), as

well as their organic counterpart (9), are reported. These organic and organometallic

chromophores show large quadratic and cubic nonlinear optical (NLO) properties. The

electrochemical properties of 13 and 16 were assessed by cyclic voltammetry, and the

linear optical, second- and third-order NLO properties were measured by UV-vis,

hyper-Rayleigh scattering studies at 1064 nm, broad spectral range femtosecond Z-

scan studies, and optical limiting studies. The Ru complexes enhance the β value by

almost 3 times compared to that of the non-Ru-containing counterparts. However, the

introduction of a meso-substituted porphyrin-based bridge has a limited effect on

quadratic and cubic NLO responses compared to phenylene bridge-based Ru

complexes [1], which can be explained by the strong linear absorption of the porphyrin

at the measurement wavelength. Optical limiting measurements showed reverse

saturable absorption properties of 13 and 16.

References

[1] Organometallic Complexes for Nonlinear Optics. 43. Quadratic Optical Nonlinearities of Dipolar

Alkynylruthenium Complexes with Phenyleneethynylene/Phenylenevinylene Bridges

Luca Rigamonti, Bandar Babgi, Marie P. Cifuentes, Rachel L. Roberts, Simon Petrie, Robert Stranger,

Stefania Righetto, Ayele Teshome, Inge Asselberghs, Koen Clays, and Mark G. Humphrey

Inorganic Chemistry 2009 48 (8), 3562-3572

DOI: 10.1021/ic801953z



Desulfination versus decarboxylation as a means of

generating three- and five- coordinate organopalladium

complexes [(phen)nPd(C6H5)]+ (n = 1 and 2) to study their

fundamental bimolecular reactivity.

Zilin Wang[1], Yang Yang[1], Paul S. Donnelly[1], Allan J. Canty[2]*, Richard A. J.

O’Hair[1]*

[1] School of Chemistry, The University of Melbourne

[2] School of Natural Sciences – Chemistry, University of Tasmania

Routes to the formation of the 1,10-phenanthroline (phen) ligated organopalladium

complexes [(phen)Pd(C6H5)]+ and [(phen)2Pd(C6H5)]+ via thermal extrusion of CO2 or

SO2 from mono-nuclear, mono-carboxylate or sulfinate complexes

[(phen)nPd(O2XC6H5)]+ (X = C or S; n = 1 and 2) are examined using a combination of

low energy collision induced dissociation (CID) experiments in an ion trap mass

spectrometer and DFT calculations. [(phen)Pd(C6H5)]+ is formed from both

[(phen)Pd(O2CC6H5)]+ and [(phen)Pd(O2SC6H5)]+ (eq. 1) but only

[(phen)2Pd(O2SC6H5)]+ fragments to form [(phen)2Pd(C6H5)]+ (eq. 2). In contrast,

[(phen)2Pd(O2CC6H5)]+ fragments via loss of a phen ligand to form

[(phen)Pd(O2SC6H5)]+ (eq. 3). The experimental findings are supported by DFT

calculations, which show that the barriers associated with the desulfination reactions

are lower than those for the decarboxylation reactions. Of the organopalladium cations

[(phen)Pd(C6H5)]+ and [(phen)2Pd(C6H5)]+, only the three-coordinate complex reacts

with pyridine via a ligand coordination reaction to yield [(phen)Pd(C6H5)(NC5H4)]+ and

with formic acid via an acid-base reaction to form [(phen)Pd(O2CH)]+. DFT calculations

highlight that the former reaction is exothermic by 44 kcal/mol while the later reaction

proceeds via a favorable six-centered transition structure.

[(phen)Pd(O2XC6H5)]+ → [(phen)Pd(C6H5)]+ + XO2 (1)

[(phen)2Pd(O2XC6H5)]+ → [(phen)2Pd(C6H5)]+ + XO2 (2)

→ [(phen)Pd(O2XC6H5)]+ + phen (3)

(X = C or S)



Early transition metal poly(methimazolyl)borate complexes

Steven S. Welsh, Anthony F. Hill*

ANU Research School of Chemistry, Australian National University, Sullivans Creek

Road, Acton, ACT, 2601

Poly(methimazolyl)borates HχB(mt)4-χ are a class of chelating ligands which have the

ability to bind to a metal centre via two or three ‘soft’ sulphur donor atoms. They

possess excellent donor properties for late transition metals, in accordance with the

hard-soft acid-base concept, where nigh-ideal ‘soft acid/soft base’ compatibility is

observed.

However, a growing body of evidence suggests that binding to early ‘hard’ transition

metals in high oxidation states may not only be viable, but also more readily achievable

than previously thought. The first such exemplar species, [M(=NR)Cl2{HB(mt)3}] (M =

Nb, Ta; R = C6H3iPr2-2,6; mt = methimazolyl), Cp[HB(mt)3]ZrCl2 and

[Ti(=NCMe3){H2B(mt)2}2], display a range of poly(methimazolyl)borate coordination

modes and demonstrate the first signs of a field of chemistry which up until now has

been untapped. [1-3]

Initial efforts to synthesise early transition metal poly(methimazolyl)borates were

significantly hindered. In an effort to overcome many of these hurdles, our current work

hopes to improve on the synthetic methodologies which currently exist, and to develop

new synthetic pathways which will ultimately lead to a greater diversity and

understanding in this field.

Simplified molecular structures of Cp[HB(mt)3]ZrCl2[2] and [Ti(=NCMe3){H2B(mt)2}2][3].

References

[1] A. F. Hill, A. D. Rae, M. K. Smith, Inorg. Chem., 2005, 44, 7316

[2] D. Buccella, A. Shultz, J. G. Melnick, F. Konopka, G. Parkin, Organometallics, 2006, 25, 5496

[3] A. F. Hill, M. K. Smith, Dalton Trans., 2006, 28

B1

S3

S1

S2

Zr1

S22 S21

S12 S11

B2

B1

Ti1



A novel transition-metal assisted approach to amide

synthesis directed by mechanistic studies

Yang Yang, Paul S. Donnelly, Allan J. Canty, Richard A. J. O’Hair*

School of Chemistry and Bio21 Molecular Science and Biotechnology Institute,

University of Melbourne

Amides are a basic and highly important class of compounds with a variety of biological

activities. As most of methods for amide synthesis generate a large amount of waste

and suffer from low atom efficiency, a more environmentally friendly, safe and highly

atom-efficient method is still needed.

A palladium catalysed synthesis of amides from aromatic carboxylic acids and

isocyanates (RNCO) is investigated as an adaption of the CO2 ExIn (ExIn = Extrusion-

Insertion) reactions developed for the synthesis of thioamides from carboxylic acids

and isothiocyanates (RNCS).[1] Multistage mass spectrometry (MSn) experiments for

model systems established “proof of concept” demonstrating decarboxylation of

[(L)nPd(O2CAr)]+, to give [(L)nPdAr]+, followed by reaction with an isocyanate, to yield

[(L)Pd(NRC(O)Ar)]+. DFT calculations predicted these reactions to be highly

exothermic and occur via isocyanate insertion into the Pd-C bond.

The individual reaction steps associated with the conversion of 2,6-dimethoxybenzoic

acid into amides in solution was probed by 1H NMR spectroscopy as was the use of

stoichiometric amounts of Pd(O2CCF3)2 and isocyanates. The best identified reaction

conditions for this one-pot method gave moderate to high yields of amide depending

on the isocyanate employed.

A mechanistic understanding obtained from these model studies encouraged

development of a solution phase synthesis of amides using a catalytic amount of

palladium. Based upon previous work, a one-pot catalytic microwave protocol was

investigated in which palladium salts, ligands and solvent were screened. The use of

Pd(O2CCF3)2, 6-methyl-2,2’-bipyridyl and trifluoracetic acid (TFA) in N-methyl-

pyrrolidinone (NMP) provided the corresponding amides in 63-84% yields.

References

[1] A. Noor, J. Li, G. N. Khairallah, Z. Li, H. Ghari, A. J. Canty, A. Ariafard, P. S. Donnelly and R. A. J.

O’Hair,Chem. Commun., 2017, 53, 3854-3857.



Reductive Trimerization of CO to the Deltate Dianion using

Activated Magnesium(I) Compounds

K. Yuvaraj,† Iskander Douair,‡ Albert Paparo,† Laurent Maron,‡ Cameron Jones*,†

†School of Chemistry, Monash University, Melbourne, VIC, 3800, Australia

‡ Université de Toulouse et CNRS, INSA, UPS, F-31077 Toulouse, France

Carbon monoxide is a cheap and abundant industrial feedstock. In combination with

H2 (i.e. in synthesis gas: CO/H2) it is utilized as a versatile C1 building block in, for

example, the Fischer-Tropsch (F-T) process.[1] In order to model the fundamental

steps of the F-T process, recent interest has lain with the reductive homologation of

CO (possessing one of the strongest bonds known (BDE = 257 kcal/mol)[2]) with low-

valent organometallic compounds, yielding cyclic and acyclic oxocarbon anions, e.g.

ethynediolate [C2O2]2- and cyclic aromatics [CnOn]2- (n = 3-6), under mild conditions.

In this context, the first molecular Mg(I) complexes were synthesised in 2007, and have

been shown to be versatile reducing agents,[3] but they do not couple CO. 1:1 reactions

of magnesium(I) complexes with NHCs or DMAP (4-dimethylaminopyridine) yield

unsymmetrical magnesium(I)-adduct complexes, [(L)(D)Mg−Mg(L)] (L = -

diketiminate) which markedly increase the Mg−Mg bond distances of the systems.

Interestingly, two of these highly activated species are shown to reductively trimerize

CO to yield rare crystallographically characterised examples of the planar, aromatic

deltate dianion, incorporated in the complexes [{(L)(D)Mg}(-C3O3){Mg(L)}]2 (Scheme

1)[4].

Scheme 1. Synthesis of deltate complexes.

References

[1] a) A. Y. Khodakov, W. Chu, P. Fongarland, Chem. Rev. 2007, 107, 1692; b) C. K. Rofer-

DePoorter, Chem. Rev. 1981, 81, 447.

[2] R. Kalescky, E. Kraka, D. Cremer, J. Phys. Chem. A 2013, 117, 8981.

[3] a) S.P. Green, C. Jones, A. Stasch, Science 2007, 318, 1754.

[4] K. Yuvaraj, I. Douair, A. Paparo, L. Maron, C. Jones, 2019 (Manuscript submitted).



Towards High-Generation Ruthenium Alkynyl Dendrimers

for Nonlinear Optics

Ling Zhang, Mahbod Morshedi, Mark G. Humphrey*

Research School of Chemistry, Australian National University, Canberra ACT 2601,

Australia. E: [email protected]

Materials with nonlinear optical properties (NLO), especially multi-photon absorption

(MPA) properties are of significant interest for applications such as microfabrication,

bioimaging, photodynamic therapy, and frequency up-conversion lasing [1]. Studies

showed ruthenium alkynyl dendrimers demonstrated promising potential for MPA

properties [2-4]. A series of third-generation ruthenium alkynyl dendrimers and zero-,

first and second-generation homologues were synthesized. The size, purity, and

structural features of the dendrimers were assessed by a combination of 31P NMR

spectroscopy, diffusion-ordered spectroscopy (DOSY) [5], size-exclusion

chromatography (SEC), HR-ESI mass spectrometry, and transmission electron

microscopy (TEM).

Ruthenium alkynyl dendrimers of zero-, first-, second- and third-generations

References

[1] He, G. S.; Prasad, P. N., et al., Chem. Rev., 2008, 108, 1245-1330.

[2] Green K A, Humphrey, M. G., et al., Macromol. Rapid Comm., 2012, 33, 573-578.

[3] Simpson, P. V.; Humphrey, M. G. et al., Angew. Chem. Int. Ed., 2016, 55, 2387-2391.

[4] McDonagh, A. M.; Humphrey, M. G., et al., J. Am. Chem. Soc., 1999, 121, 1405-1406.

[5] Evans R, Morris G. A., et al. Angew. Chem. Int. Ed., 2013, 52, 3199-3202.


List of Attendees for the 12th Australasian Organometallics Meeting (OZOM12),

School of Chemistry, The University of Melbourne, 9th – 12th July 2019

First name Surname Institution

Aidan Matthews Monash University

Aidan McKay University of Otago

Alasdair McKay The University of Melbourne

Alexander Bissember University of Tasmania

Allan Canty University of Tasmania

Alphonsine Ngo Ndimba Australian National University

Angelo Frei The University of Queensland

Angus Shephard James Cook University

Angus Gillespie The University of Western Australia

Annie Colebatch University of Cambridge

Anthony Hill Australian National University

Asif Noor The University of Melbourne

Becky Fuller Curtin University

Benjamin Frogley Australian National University

Brendan Abrahams The University of Melbourne

Carol Hua The University of Melbourne

Cheesheng Onn Australian National University

Chiara Caporale Curtin University

Chuanzhu Gao Monash University

Colette Boskovic The University of Melbourne

Cory Smith Monash University

Curtis Ho University of Tasmania

Dafydd Jones Monash University

Daniel Harrison The University of Western Australia

Daniel Van Zeil Monash University

Daven Foster The University of Western Australia

David McMorran University of Otago

Declan Burke The University of Western Australia

Dr. Albert Paparo Monash University

Drasko Vidovic Monash University

Frank T. Edelmann Otto von Guericke University Magdeburg

Frederic PAUL Institut des Sciences Chimiques de Rennes

George Laffan Australian National University

George Koutsantonis The University of Western Australia

Glen Deacon Monash University

Guy Jameson The University of Melbourne

Harrison Barnett Australian National University

Howard Ma The University of Melbourne

Huan Wang Australian National University


Ian Rae The University of Melbourne

Isabelle Dixon Universite Toulouse III Paul Sabatier

James Findlay University of Otago

Jamie Hicks Australian National University

Jamie Greer Monash University

Jeremy Stone The University of Western Australia

Jian-Zhong Wu The University of Western Australia

Jun Du Australian National University

Kirralee Burke Monash University

Koushik Venkatesan Macquarie University

Lachlan Watson Australian National University

Lachlan Barwise La Trobe University

Lachlan Sharp-

Bucknall

La Trobe University

Lachlan McInnes The University of Melbourne

Liam Burt Australian National University

Liam Stephens Monash University

Ling Zhang Australian National University

Lou Rendina The University of Sydney

Lynn Lisboa University of Otago

Maggie Aulsebrook Australia’s Nuclear Science and Technology

Organisation (ANSTO)

Mahbod Morshedi Australian National University

Marcus Korb The University of Western Australia

Mark Humphrey Australian National University

Mark Rizzacasa The University of Melbourne

Masnun Naher The University of Western Australia

Matthew Gyton University of Warwick

Max Massi Curtin University

Max Roemer Macquarie University

Megan Herdman Monash University

Melissa Werrett Monash University

Michael Hall The University of Western Australia

Michael Stevens Monash University

Mohammad Al Bayer La Trobe University

Monica Perez-

Temprano

Institute of Chemical Research of Catalonia

Nicholas Tan Curtin University

Nick Cox Australian National University

Nigel Lucas University of Otago

Nilan Withanage La Trobe University

Nimrod Eren Monash University


Palak Garg Monash University

Parvin Safari The University of Western Australia

Paul Low The University of Western Australia

Paul Donnelly The University of Melbourne

Penelope Brothers Australian National University

Peter Junk James Cook University

Quinn van Hilst University of Otago

Rachel Steen University of York

Rebekah Duffin Monash University

Richard O'Hair The University of Melbourne

Richard Manzano Australian National University

Robert Malmberg Macquarie University

Ryan Huo Monash University

Samantha Orr Monash University

Sarmi Munuganti Monash University

Seyed

Mohammad

Bagher

Hosseini

Ghazvini

The University of Western Australia

Shazia Nawaz Monash University

Sigridur Suman University of Iceland

Sinead Keaveney Macquarie University

Sneha Mullassery Monash University

Stacey Rudd The University of Melbourne

Stephen Best The University of Melbourne

Steven Welsh Australian National University

Stuart Batten Monash University

Victoria Blair Monash University

Weam Altalhi The University of Melbourne

William Erb Université de Rennes 1

Yang Yang The University of Melbourne

Yong-Shen Han Australian National University

Yu Qing Tan Monash University

Yuvaraj Kuppusamy Monash University

Zhifang Guo Monash University

Zilin Wang The University of Melbourne

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