Centre for Organometallic Chemistry

Dr. R. Ramesh

Professor and Coordinator

Genesis

Organometallic chemistry lies at the interface between classical organic and inorganic

chemistry which provides a common platform for both organic and inorganic chemists to work

under a single roof. This field has provided a series of important conceptual insights and

surprising structures. The sustained interest in the area is due to the application of

organometallic compounds in selective organic synthesis, particularly in the development of

industrially important, high-performance, homogeneous catalysts and the enormous potential

of organometallics as precursors in the production of new advanced materials such as sensors,

switches and other types of solids with important, nonlinear optical properties. Further, bio-

organometallic chemistry is an emerging field of research and, in particular, the use of

organotransition metal complexes as potential anticancer agents appears to be promising.

About the centre

In appreciation of the contributions made by the research group under the leadership of

Prof. R. Ramesh, Bharathidasan University has approved the proposal for the creation of a

Centre and thereby the ‘Centre for Organometallic Chemistry’(COMC)was established in the

year 2016.The Centre has been supported by various national funding agencies like UGC, CSIR,

DST-SERB. Further, Indo-French Center for Promotion of Advanced Research (IFCPAR), New

Delhi has sanctioned an amount of Rs.1.90 crores under the scheme of collaborative research

project, with Dr. David Semeril and Dr. Domnique Matt, Laboratory of Molecular Inorganic

Chemistry and Catalysis, University of Strasbourg, France. This project offers exchange visits for

both Principal Investigators and research scholars for three years. At present the centre has

instruments facilities such as GC-MS, GC, Electrochemical analyser, Schlenk line set- up,

Rotavapours and some more will be acquired.

Mission

COMC encourages the development of novel and innovative ideas and solutions in the

field of organometallic chemistry and to generate new materials for various applications.

Vision

Our Centre (COMC) is dedicated to

Promote the development of innovative research programs

Perform high-quality research in the field of organometallic chemistry

Sensitize a diverse population of students towards this area of research

Develop the strategic partnerships with chemical industry, pharmaceuticals, research

laboratories spread over the country

Extending the Centre’s facilities for campus and external users

Produce knowledgeable graduates for careers in academia, industry and Government sectors

Encourage participation of young students in seminars/ workshops/conferences

Objectives

The main objectives of the Centre involve,

Design and synthesize of new platinum group metals based organometallic compounds

Generation of active and recyclable catalysts for organic transformations

Organic synthesis via organometallic compounds

Development of potential metallo drugs

New materials such as sensors, switches, nanomaterials for diverse applications.

Synthesis

Centre for Organometallic Chemistry is mainly focusing on the synthesis of platinum

group of organometallic complexes containing various multidendate ligands.These compounds

have attracted much attention in organic synthesis, catalysis, materials and biology. In light of

this, we have been actively working in the synthesis of Ru, Rh, Pd, Pt and Ni based complexes of

carbonyls, tripodals, pincers, NHC, resorcin[4]arene, Schiff bases including TSC, hydrazones.

Further, severalsub areas in this field were identified to advance environmentally friendly and

sustainable processes and the research work is in progress.

Ru-Pincer complex

complexes

Pd-(Bis) TSC

complex

Metal mediated organic synthesis

Transition metals especially platinum

group metals open up new opportunities for

organic synthesis. In search for unconventional

and efficient approach towards metal mediated

organic synthesis, our research group is actively

involved in the development of flexible, efficient

and environmental benign catalytic protocols

for the synthesis of organic compounds,

intermediates and pharmaceutically important

targets. Our research group is engaged in the

development of several new Ru catalysts for

greener synthesis of amides and imines and Pd

catalysts for C-C, (Suzuki-Miyaura, Heck), C-N

(Buchwald-Hartwig), C-O, coupling reactions

and various other reactions. Organic

compounds were synthesized in excellent yield

with low loading catalysts with high TON/TOF.

Further, our goal is to develop new class of

organometallic catalysts, which are expected to

find widespread applications in the synthesis of

organic materials and bioactive compounds.

Catalytic organic transformations

Organometallic catalysts are able to efficiently

promote different organic transformations. In this

class, ketones and imines to alcohols/amines

(transfer hydrogenation), alcohols to carbonyl

compounds (oxidation), aldehydes to amides and

olefin to aldehydes (oxidation) are powerful method

for the synthesis of fine chemicals for both

laboratory and industrial applications. In particular,

ruthenium and rhodium catalyst containing pincer,

Schiff base, thioamide, hydrazone and

thiosemicarbazone ligands have proven to be

effective catalysts for above organic

transformations. Recently, we have developed

ruthenium(II), ruthenium(III) and rhodium(III)

catalysts for many organictransformations.

Investigations are going on to improve catalytic

activity with high product yield in open atmosphere,

without usadditives. Notably, these protocol works

well with ultra- low loading of catalysts with high

turnover numbers in short time towards different

substrates.

Pd- hydrazone

complex

Ru-hydrazone

complex

Rh-Pincer complex

Cyclometallated Ru- TSC

complex

Bio-organometallic chemistry

Bioorganometallic chemistry is an

emerging area in chemical biology due to varied

biological applications of organometallic

compounds.Our current research goal is to design

and study novel cytotoxic organometallic

complexes for targeted therapeutic and diagnostic

applications. We are engaged in the synthesis and

development of specifically targeted cytotoxic

metal complexes such as Cu, Ru, Ni for various

therapeutic and diagnostic applications. Their

detailed binding interaction studies with biological

targets (nucleic acid, proteins etc.) and fate in

biological medium were also investigated. Recently

we have reported several ruthenium(II) arene

complexes with excellent cytotoxicity than

cisplatin against many human cancer cell lines and

act as potential apoptosis inducers. Our primary

objective is to generate active metallo drugs for

various cancers without side effects.

New materials

The research interests of the COMCincludes

the preparation of inorganic, organic and polymer

materials and to study of their performances in

sensors, energy storage and, fluorescence

materials and imaging and various biomedical

applications. Many organoruthenium(II)

complexes have been reported form our laboratory

and are promising fluorescence materials at room

temperature with high quantum yield.

Development of new pincer ruthenium complexes

is under progress towards their material science

applications such as sensors, molecular switches

etc.

Half-sandwich Ru-hydrazone complex

Cyclometallated Ru-azo complex

Instruments Facilities

GAS CHROMATOGRAPH MASS SPECTROMETER

(SHIMADZU GC-MS QP 2010 SE)

GAS CHROMATOGRAPH

(BRUKER SCION 436-GC)

ELECTROCHEMICAL ANALYSER - SCANNING

POTENTIOSTAT (CH INSTRUMENTS CHI600E)

ROTAVAPOR-II

(BUCHI V-801 EACYVAC VACUUM MODULE)

SCHLENK LINE

(NITROGEN LINE)

Group Members

T.S. Manikandan DST-SERB (JRF) manitshp01@gmail.com

Research Area: Catalytic organic transformations promoted by ruthenium(II) and palladium(II) complexes

N. Mohan BSR-RFSMS (SRF) mohanchem17@gmail.com

Research Area: Catalytic and biological applications of ruthenium half-sandwich arene complexes

S. Balaji INDO-FRENCH (JRF) sunderbalajichem@gmail.com

Research Area: Influence of the Resorcin[4]arene on the catalytic outcomes

G. Balamurugan CSIR (SRF) balamurugan87@bdu.ac.in

Research Area: Transition metal complexes bearing N-heterocyclic carbenes and their catalytic application in organic transformations

S. Saranya DST-INSPIRE (SRF) saransundar66@yahoo.com

Research Area: Investigation of catalytic activities of mono- and di-nuclear ruthenium complexes

V. Tamil thendral DST-SERB (JRF) tamilthendralphd@gmail.com

Research Area: Development of organoruthenium catalysts for organic synthesis

Dr. T. Sathiya Kamatchi SERB-NPDF sathyaachemist@gmail.com

Research Area: Ruthenium based anticancer drugs

Alumni

Dr. G. Venkatachlam-2005

Postdoctoral Research: University of Fribourg, Switzerland & Kookmin University, South Korea Current Position: Assistant Professor Govt Arts College Dharmapuri, Tamil Nadu, India.

Dr. R. N. Prabhu-2012 Postdoctoral Research: University of Hyderabad

Current Position: Assistant Professor Bishop Heber College,

Tiruchirappalli Tamil Nadu, India.

Dr. K. Naresh Kumar-2006 Postdoctoral Research: University

of Zurich, Switzerland Current Position:

Research Manager Indian Oil Corporation Limited New Delhi, India.

Dr. E. Sindhuja-2015 Current Position: Assistant professor Sri Paramakalyani College Alwarkurichi, Tirunelveli

Tamil Nadu, India.

Dr. S. Kannan-2008 Postdoctoral Research: Kookmin University, South Korea

Current Position: Research Manager Indian Oil Corporation Limited

New Delhi, India.

Dr. A. K. Devi-2015 Current Position: Assistant professor Vivekanandha College for Women, Namakkal Tamil Nadu, India

Dr. M. Ulaganatha Raja-2011 Postdoctoral Research: University

of Neuchatel, Switzerland Current Position:

Assistant Professor SVN College, Nagamalai

Madurai, Tamil Nadu, India.

Dr. M. Subarkhan-2017 Current Position:

Zhejiang University, PR China Postdoctoral Researcher

Dr. N. Raja-2012 Postdoctoral Research: University of Neuchatel, Switzerland

Current Position: Assistant Professor Anna University constituent College, Ariyalur, Tamil Nadu, India.

Dr. R. Raj Kumar-2017 Current Position: Postdoctoral Researcher Xian Jiatong University PR China

Dr. D. Pandiarajan-2012 Postdoctoral Research: University of Zurich, Switzerland

Current Position: Assistant Professor Jain University Bengaluru, India.

Dr. S. Muthumari-2019 Current Position: Postdoctoral Researcher IIT-Bombay, Mumbai.

Research Projects

Sl. No

Title of Project PI / Co-PI

Amount (Rs. In Lakhs)

Year of Completion

Funding Agency

1 Ru(II) Schiff base complexes: Synthesis, Characterisation and antimicrobial activity

PI 0.14 2001 UGC

2 Novel Ru(III) complexes of multidentate ligands: Synthesis, spectra, electrochemistry and bioactivity

PI 5.40 2002-2005 CSIR

3 New families of Ru(II) carbonyl complexes: Synthesis, spectra, redox and catalytic properties

PI 4.42 2003-2006 UGC

4 Synthesis of Uranium and Mercury Phosphoylide complexes: Reactivity towards carbonyl compounds, isocyanides and deprotonating agents

Co-PI 3.84 2004-2007 DST

5 Development of novel ruthenium pincer organometallic catalysts: Synthesis, structure and Catalytic transfer hydrogenation

PI 18.96 2007-2010 DST

6 Novel organo-ruthenium(III) metalla-cycles: New catalysts for transfer hydrogenation ketones

PI 14.36 2008-2011 CSIR

7 Novel binuclear ruthenium(III) complexes: Synthesis, structure, spectral, magnetic and electrochemical Properties

PI 8.25 2011-2014 UGC

8 Ru(II) complexes featuring N-heterocyclic carbenes: Synthesis, structure, redox properties and catalytic applications

PI 23.0 2013- 2016 CSIR

9 A new series of Ru(II) and Pd(II) aroylhydrazone complexes: Synthesis, structure, catalytic applications to transfer hydrogenation and carbon-carbon coupling reactions

PI 40.0 2013- 2016 SERB

10 Influences of the resorcin [4] arene on the catalytic outcomes

PI 189.64 2013- 2016 Indo-French

11 Development of new organoruthenium catalyst for direct synthesis of amide and amines/imines from dehydrogenation of alcohols

PI 32.0 2017-2020 SERB

International Research Collaborations

1. Phong University of Science and Technology, South Korea. 2. University of Strasbourg, France. 3. Institute of High Energy Physics, China. 4. University of Zurich, Swiss. 5. University of Silesia, Poland.

National Research Collaborations

1. Indian Institute of Chemical Biology (CSIR), Kolkata. 2. Indian Institute of Science (IISc), Bangaluru. 3. University of Hyderabad, Hyderabad. 4. Bharathiar University, Coimbatore. 5. Cochin University of Science and Technology (CUSAT), Kochi. 6. Indian Institute of Technology (IIT), New Delhi. Selected Publications

1. Direct Synthesis of 2,4,5-Trisubstituted Imidazoles from Primary Alcohols by Diruthenium(II) Catalysts under Aerobic Conditions S. Saranya and R. Ramesh*, Org. Biomol. Chem., 17 (2019) 1402. (IF: 3.564)

2. The Tandem C-H/N-H Activation of N-methyl Arylamide Catalysed by Dinuclear Pd(II)

Benzhydrazone complex: A Concise Access to Phenanthrodinone. T. S. Manikandan, R. Ramesh*, D. Semeril, Organometallics, 38 (2019) 319. (IF: 4.051)

3. Synthesis and Structures of Arene Ruthenium(II)-NHC complexes: Efficient catalytic α-

alkylation of ketones via hydrogen auto transfer reaction. G. Balamurugan, S. Balaji, R.Ramesh* and N. Bhuvanesh, Appl. Organomet. Chem., 33 (2019) 4696. (IF: 3.581)

4. Chiral calixarene and resorcinarene derivatives: Conical cavities substituted at their

upper rim by two phosphito units and their uses as ligands in Rh- catalysed hydroformylation. N. Natarajan, M. Pierrevekin, D. Semeril, C. Bauder, D. Matt and R. Ramesh, Catalysis Commun., 118 (2019) 70. (IF: 3.463)

5. Synthesis and structure of arene ruthenium(II) complexes: one pot catalytic approach to

synthesis of bioactive quinolines under mild condition. S. Muthumari, S. Saranya and R. Ramesh*, Appl. Organomet. Chem., 32 (2018) 4582. (IF: 3.581)

6. Synthesis and structure of arene ruthenium(II) benzhydrazone complexes:

Antiproliferative activity, apoptosis induction and cell cycle analysis R. Raj Kumar, R. Ramesh* and G. Malecki, J. Organomet. Chem., 862 (2018) 95. (IF: 1.946)

7. Synthesis and structure of Ru(II) complexes of thiosemicarbazones: Highly selective

catalysts for oxidation of olefins to aldehydes. S. Muthumari and R. Ramesh*, ChemistrySelect 3 (2018) 3036. (IF: 1.505)

8. Direct aerobic strategy for selective synthesis of imines via alcohols and

aminespromoted by ruthenium(II) (η6-cymene) complexes T. S. Manikandan, S. Naveen, N. Loknath and R. Ramesh*, ChemistrySelect, 3 (2018) 1561. (IF: 1.505)

9. Synthesis, antiproliferative activity and apoptosis promoting effects of arene Ru(II)

complexes with N, O chelating ligands N. Mohan, M.M. Khan and R. Ramesh*, J. Organomet. Chem., 859 (2018) 124. (IF: 1.946)

10. Synthesis and structure of new binuclear ruthenium(II) arene benzyl

bis(benzoylhydrazone) complexes: Investigation on antiproliferative activity and apoptosis induction M. Subarkhan, S. Saranya, and R. Ramesh*, Inorg. Chem. Front., 5 (2018) 585. (IF: 5.106)

11. Cavitand chemistry: nickel half-sandwich complexes with imidazolylidene ligands

bearing one or two resorcinarenyl substituents N. Natarajan, T. Chavagnan, D. Sémeril*, E. Brenner, D. Matt, R. Ramesh, and L. Toupet, Eur. J. Inorg. Chem., (2018) 890. (IF: 2.507)

12. Cyclometalated Ru(II)-NHC complexes as effective catalysts for transfer hydrogenation:

Influence of wintip group on catalytic outcomes G. Balamurugan, R. Ramesh* and G. Małecki., ChemistrySelect, 2 (2017) 10603. (IF: 1.505)

13. One-pot catalytic approach for the selective aerobic synthesis of imines from alcohols

and amines using efficient arene diruthenium(II) catalysts under mild condition S. Saranya, R. Ramesh* and G. Małecki., Eur. J. Org. Chem., (2017) 6726. (IF: 2.882)

14. Versatile coordination ability of thioamide ligand in Ru(II) complexes: synthesis,

computational studies, in vitro anticancer activity and apoptosis induction R. Raj Kumar, R. Ramesh* and G. Malecki, New. J. Chem., 41 (2017) 9130. (IF: 3.201)

15. Transfer hydrogenation of ketones catalyzed by half-sandwich (η6-p-cymene)

ruthenium(II) complexes incorporating benzoylhydrazone ligands N. Mohan, S. Muthumari and R. Ramesh*, Appl. Organomet. Chem., 31(2017) 3648. (IF: 3.581)

16. Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex:

catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids

R. N. Prabhu and R. Ramesh*, Tetrahedron Lett., 58 (2017) 405. (IF: 2.125) 17. Ru(II) carbazole thiosemicarbazone complexes with four membered chelate ring:

Synthesis, molecular structures and evaluation of biological activities R. Raj Kumar, R. Ramesh* and G. Malecki, J. Photochem.Photobiol B: Biol. 165 (2016) 310. (IF: 3.165)

18. Steric control on the coordination behaviour of carbazole thiosemicarbazones towards

[RuH(Cl)(CO)(AsPh3)3]: A combined experimental and theoretical study R. Raj Kumar, R. Ramesh and G. Malecki, New. J. Chem., 40 (2016) 10084. (IF: 3.201)

19. Synthesis and molecular structure of arene ruthenium(II) benzhydrazone complexes: Impact of substitution at chelating ligand and arene moiety on antiproliferative activity

M. Mohamed Subarkhan, R. Ramesh, Y. Liu, New J. Chem., 40 (2016) 9813. (IF: 3.201) 20. Synthesis and characterization of cycloruthenated benzhydrazone complexes: Catalytic

applications to selective oxidative cleavage of olefins to aldehyde. T.S. Manikandan, R. Ramesh, D. Semeril, RSC Adv., 6 (2016) 97107. (IF: 2.936)

21. Square-planar Ni(II) thiosemicarbazonato complex as an easily accessible and

convenient catalyst for Sonogashira cross-coupling reaction R. N. Prabhu and R. Ramesh*, Tetrahedron Lett., 57 (2016) 4893. (IF: 2.125)

22. Ruthenium(II) Arene Complexes Containing Benzhydrazones: Synthesis, structure and

Antiproliferative Activity M. Mohamed Subarkhan and R. Ramesh*, Inorg. Chem. Front., 3(2016) 1245. (IF: 5.106)

23. Synthesis and catalytic evaluation of ruthenium(II) benzhydrazone complex in transfer

hydrogenation of ketones T. S. Manikandan, S. Saranya, R. Ramesh*, Tetrahedron Lett., 57 (2016) 3764. (IF: 2.125)

24. Highly efficient palladium(II) hydrazone based catalysts for the Suzuki coupling reaction

in aqueous medium S. Muthumari and R. Ramesh*, RSC Adv., 6 (2016) 52101. (IF: 2.936)

25. Antiproliferative activity of cationic and neutral thiosemicarbazone copper(II)

complexes M. Mohamed Subarkhan, R. N. Prabhu, R. Raj Kumar and R. Ramesh*, RSC Adv., 6 (2016), 25082. (IF: 2.936)