alkali and alkaline earth metals

17
Alkali and alkaline earth metals Michael S. Hill DOI: 10.1039/b716559p The aim of this chapter is to reflect major advances in the coordination and organometallic chemistry of the alkali and alkaline earth elements that appeared in peer-reviewed journals throughout 2007. These self-imposed limitations necessarily result in the omission of a great number of note- worthy advances in related fields rooted in either solid-state, materials or theoretical chemistry. The author apologises in advance, therefore, that not all published work can be afforded the same depth of coverage. Highlights The undoubted highlight of 2007 occurred toward the end of the year with the report by Jones and Stasch of the first stable magnesium(I) compounds containing a Mg– Mg bond. Other highlights include the first magnesium boryls and the continued growth of the fundamental and applied chemistry of calcium coordination com- plexes. 1. Introduction The stability of magnesium carbenoids and several new reactions based on the electrophilicity of the magnesium carbenoids, including 1,3-CH insertion, have been reviewed. 1 The role of alkali metal cation complexants in the synthesis of alkalides and electrides has been reviewed and discussed. 2 Group 1 and 2 ‘ate’ compounds have been the subject of a review which covers selected syntheses made possible by their application as deprotonation reagents. 3 Recent advances in the growing field of calcium aryl chemistry have also been summarised in two separate reviews. 4,5 The mechanistic complexity with which lithium diisopropylamide metalates organic substrates through a variety of mechanisms has been summarised, with particular attention paid to the influence of solvation and aggregation on reactivity. 6 A comprehensive review of metal hydrides, including those of Groups 1 and 2, for hydrogen storage has appeared. 7 2. Lithium The simplest possible chemical reduction process, the reaction of lithium atoms in solid H 2 has yielded the highly ionic rhombic dimer [(LiH) 2 ]. [(LiH) n ] oligomers have also been investigated and have been suggested as having the potential to act as a useful source of H 2 gas. 8 Department of Chemistry, University of Bath, Claverton Down, Bath, UK. E-mail: [email protected]; Fax: +44(0)1225 386231; Tel: +44(0)1225 383394 64 | Annu. Rep. Prog. Chem., Sect. A, 2008, 104, 64–80 This journal is c The Royal Society of Chemistry 2008 REVIEW www.rsc.org/annrepa | Annual Reports A Published on 30 April 2008. Downloaded by Lomonosov Moscow State University on 20/11/2013 01:48:50. View Article Online / Journal Homepage / Table of Contents for this issue

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Alkali and alkaline earth metals

Michael S. HillDOI: 10.1039/b716559p

The aim of this chapter is to reflect major advances in the coordination andorganometallic chemistry of the alkali and alkaline earth elements thatappeared in peer-reviewed journals throughout 2007. These self-imposedlimitations necessarily result in the omission of a great number of note-worthy advances in related fields rooted in either solid-state, materials ortheoretical chemistry. The author apologises in advance, therefore, that notall published work can be afforded the same depth of coverage.

Highlights

The undoubted highlight of 2007 occurred toward the end of the year with the report

by Jones and Stasch of the first stable magnesium(I) compounds containing a Mg–

Mg bond. Other highlights include the first magnesium boryls and the continued

growth of the fundamental and applied chemistry of calcium coordination com-

plexes.

1. Introduction

The stability of magnesium carbenoids and several new reactions based on the

electrophilicity of the magnesium carbenoids, including 1,3-CH insertion, have been

reviewed.1 The role of alkali metal cation complexants in the synthesis of alkalides

and electrides has been reviewed and discussed.2 Group 1 and 2 ‘ate’ compounds

have been the subject of a review which covers selected syntheses made possible by

their application as deprotonation reagents.3 Recent advances in the growing field of

calcium aryl chemistry have also been summarised in two separate reviews.4,5 The

mechanistic complexity with which lithium diisopropylamide metalates organic

substrates through a variety of mechanisms has been summarised, with particular

attention paid to the influence of solvation and aggregation on reactivity.6 A

comprehensive review of metal hydrides, including those of Groups 1 and 2, for

hydrogen storage has appeared.7

2. Lithium

The simplest possible chemical reduction process, the reaction of lithium atoms in

solid H2 has yielded the highly ionic rhombic dimer [(LiH)2]. [(LiH)n] oligomers have

also been investigated and have been suggested as having the potential to act as a

useful source of H2 gas.8

Department of Chemistry, University of Bath, Claverton Down, Bath, UK. E-mail:[email protected]; Fax: +44(0)1225 386231; Tel: +44(0)1225 383394

64 | Annu. Rep. Prog. Chem., Sect. A, 2008, 104, 64–80

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Group 14 donor ligands

Collisional activation of the lithiated betaine cation [(CH3)3NCH2CO2Li]+ (m/z

124) in the gas phase has resulted in decarboxylation to form the lithiated ylide

[(CH3)3NCH2Li]+.9 Highly diastereoselective lithiation-substitution reactions of an

(S)-proline derived S-alkyl thiocarbamate have been accomplished and the config-

uration of the predominant alkyllithium species deduced by X-ray analysis.10 The

highly reactive aggregate [{(nBuLi)2 �PMDTA}2] crystallised out of a 2:1 mixture ofnBuLi and PMDTA providing insight into the influence of the nBuLi/PMDTA ratio

on the course of some deprotonation reactions.11 (R,R)-N,N,N0,N0-tetramethyl-1,2-

diaminocyclohexane [(R,R)-TMCDA]-coordinated alkyllithiums have been found to

crystallise as dimeric ([MeLi � (R,R)-TMCDA]2 and [iPrLi � (R,R)-TMCDA]2) or

monomeric (sBuLi � (R,R)-TMCDA) species. The high reactivity of sBuLi � (R,R)-TMCDA in deprotonation reactions has been reasoned to result from the mono-

meric structure.12 In related work, (R,R)-TMCDA has been coordinate to tBuLi to

form a monomeric molecular structure.13

Reich and co-workers have performed low-temperature rapid injection NMR

(RINMR) experiments on nBuLi and 2-methoxy-6-(methoxymethyl)phenyllithium,

to measure the relative reactivity of the different aggregates toward typical electro-

philes. The measurements were concluded to demonstrate that the difference in

reactivity between the lower and higher aggregates of organolithium reagents can be

many orders of magnitude higher than all previous estimates.14 (Tributylstannyl)-

methyl 2,2,6,6-tetramethylpiperidine-1-carboxylate has been metalated with tBuLi/

TMEDA and borylated with the mixed borate derived from (R,R)-1,2-dicyclohex-

ylethane-1,2-diol and t-butanol to give diastereomeric boronates in equal amounts.

The configurations of the boronates and the chiral methyllithiums derived from

them were deduced from a single-crystal X-ray analysis of a carbamate in which the

tributylstannyl group had been replaced by the [(1R)-menthyl]dimethylstannyl

group.15 The oxygen-incorporating compound, [{(C7H7LiO)6(THF)(m-diglyme-k-O,k-O0)}]Li2O, obtained by lithiation of 2-bromomethoxybenzene with nBuLi has

been shown to comprise of an octahedral Li6O-unit, which is additionally capped by

lithium atoms at two facing Li3 triangles.16 It has been shown that asymmetric

substitution of 2-lithiopiperidines can be achieved by dynamic resolution in the

presence of a variety of bidentate chiral amine ligands.17 An investigation into the

mechanism and stereochemistry of chiral lithium-carbenoid-promoted cyclopropa-

nation reactions by using density functional theory (DFT) methods has demon-

strated that the intramolecular cyclopropanation reactions promoted by chiral

carbenoids proceed by the methylene-transfer mechanism.18

A number of reports relevant to a mechanistic understanding of lithium cuprate

addition reactions appeared in 2007. Investigation of reactions of a variety of methyl

Gilman reagents Me2CuLi �LiX with EtI using rapid-injection NMR spectroscopy

conditions has revealed a number of formally CuIII tetracoordinate square-planar

intermediates, including lithium ethyltrimethylcuprate(III), with a surprising range of

stabilities.19 A mesityl lithium amidocuprate complex has been characterized in the

solid state and shown to adopt a head-to-tail conformation. 2D-NMR spectroscopic

studies revealed the presence of several structural isomers in solution, including a

head-to-head isomer, resulting from a Schlenk equilibrium. The presence of these

isomers was postulated to have a significant influence on heterocuprate reactivity.20

In closely related research, the same group have reported the synthesis and

characterisation of two novel tetranuclear and thermally-stable lithium arylcuprates,

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[Cu2Li2Mes4] and [Cu3LiMes4] � [Cu3LiMes4] was shown to be a highly active

promoter for the 1,4-addition of organolithiums to enones.21

The first triple-decker sandwich anion [(Z5-Cp)Li(Z5-Cp)Li(Z5-Cp)]� of lithocene

(Cp = C5H5) has been formed in the reaction of [Cp2V] with hppLi (hppH =

1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). The VRV-bonded complex

[V2(hpp)4] effectively acts as a ligand to intercept the polymeric structure of

[CpLi]N.22 An aluminium ’ate’ base, iBu3Al(TMP)Li, has been developed for regio-

and chemo-selective direct generation of functionalised aromatic aluminium com-

pounds. The mechanism of directed ortho alumination of functionalised aromatic

compounds has been found to proceed with facile formation of an initial adduct of

the base and aromatic, followed by deprotonative formation of the functionalised

aromatic aluminium compound.23 Transition-state structures involving synergic

cooperation between lithium and zinc have been identified as crucial in determining

whether directed ortho-metalation or 1,2-addition occurs in the reaction of benzoni-

trile or methyl benzoate with Me2Zn(TMP)Li or (MeLi)2.24

The first example of a Li/Cl carbenoid that is stable at room temperature has been

prepared and the electronic reasons for this unusual thermal stability discussed on

the basis of DFT calculations. The reactivity of this carbenoid was investigated in

the formation of a palladium carbene complex.25 Sekiguchi and co-workers have

shown that reduction of tetrakis(di-tert-butylmethylsilyl)disilene with 2.2 equiva-

lents of Li or Na naphthalenide in THF results in the formation of the silylene anion

radical [(tBuMe2Si)2Si]d� as extremely air- and moisture-sensitive red crystals.26

Reactions of several trimethylsiloxychlorosilanes (Me3SiO)RR0SiCl with lithium

metal have been reported to lead to mixtures of compounds dependent upon the R

and R0 substituents.27 Reaction of spirostannabifluorene with methyllithium has

been shown to give lithium pentaorganostannate, the first example of a stable

organostannate having five carbon substituents. The X-ray structural analysis

revealed a slightly distorted trigonal bipyramidal structure.28 The synthesis of

several stannole anions has been described. The reduction of hexaphenylstannole

by lithium gave the 1,2,3,4,5-pentaphenylstannole anion, which reacted with di-

haloalkanes to give the corresponding bis(1-stannacyclopentadien-1-yl)alkanes. The

reactions of a related stannole dianion with an equimolar amount of bulky alkyl,

aryl, silyl, and stannyl halides gave the corresponding stannole anions.29

Group 15 donor ligands

Lithium hexamethyldisilazide (LiHMDS), has been studied by DFT methods. Four

THF molecules were considered the highest degree of THF solvation for the

monomer and the highest possible degree of aggregation for unsolvated LiHMDS

was determined to be four.30 The lithium salt of the bis-furyl substituted disilazide

anion, LiN(SiMe2R)2 [R = 2-methylfuryl] has been examined as a ligand transfer

reagent for the synthesis of magnesium and aluminium compounds.31 Treatment of

the sterically hindered enaminoimine TbtNHC(Me)CHC(Me)NAr [Tbt = 2,4,6-

{CH(SiMe3)2}C6H2] withnBuLi provided the corresponding lithium b-diketiminate,

[Li{TbtNHC(Me)CHC(Me)NAr}], as a monomeric, solvent-free species.32 Several

compounds based on the C1-symmetric ligands [N(R)C(Ar)NPh]� [Ar = C6H4Me-4

or Ph, R = SiMe3], including the lithium benzamidinates have been prepared by

insertion of the nitrile 4-MeC6H4CN or PhCN into the N–Li bond of LiN-

(SiMe3)Ph.33 Enolizations of 2-methylcyclohexanone by LiHMDS in the presence

of three bidentate chelating ligands revealed an approximate 40-fold range of rates

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due to ligand-dependent structural differences in both the reactants and the transi-

tion structures.34 The X-ray crystal structures of a series of lithium quinolates,

lithium 8-hydroxyquinolinate (Liq), lithium 2-methyl-8-hydroxyquinolinate (Me-

Liq), and 2-phenyl-8-hydroxquinolinate (PhLiq), have been compared. Liq and

MeLiq molecules crystallise as hexamers, whereas PhLiq crystallises as a tetramer.35

Reaction of [MeNH3]Cl or [(tBuNH3)]Cl with LiAlH4 proceeds with H2 elimina-

tion, to give the imidoalanes Li2[(RN)4(AlH2)6] (R = Me or tBu). X-ray analysis of

the R = Me derivative revealed a structure in which the Li cations exist at two

distinct sites, each linked via Li(m-H)Al bridges to two [(MeN)4(AlH2)6]2� cages.36

Three Lewis base variations of the synthetically useful aluminate

[L �Li(TMP)(iBu)3Al], where L is TMPH, Et3N or PhC(QO)(NiPr2) have been

reported.37 Although it is inert towards conventional organomanganese reagents,

ferrocene can now be directly manganated by using a mixed lithium/manganese(II)

mixed dialkyl/amido reagent, [(TMEDA)Li(TMP)(R)Mn(R)] (R = CH2SiMe3).38

Sequential reaction of HTMP with nBuLi and Et2Zn has afforded unsolvated

polymer chains of EtZn(m-Et)(m-TMP)Li. The scope of this reagent in directed

ortho metalation chemistry has been tested by its reaction with N,N-diisopropyl-

naphthamide to give EtZn(m-C10H6C(O)(NiPr2)2)2Li � 2THF.39

Sequential treatment of Lewis acids with N,N0-bidentate ligands and tBuLi has

afforded a series of hydride-encapsulating alkali metal polyhedra. The guanidine

1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) in conjunction with

Me2Zn/tBuLi yielded the interstitial hydride [(hpp)6HLi8]

+[(tBu3Zn)]� �PhMe.

The mixed borohydride/lithium hydride species [(hpp)6HLi8]+[Et3BH]� and

[(hpp)6HLi8]+[(Et3B)2H]� were also synthesised through the direct combination of

hppLi with Et3BHLi.40 Reactions mediated by lithium diisopropylamide (LDA)

with added hexamethylphosphoramide (HMPA) have been described. The N-

isopropylimine of cyclohexanone lithiates via monomer-based pathways while

conjugate addition of LDA/HMPA to an unsaturated ester proceeds via di and

tetra-HMPA-solvated dimers.41

Treatment of the lithium amide Li[NPh(SiMe3)] with 2,4,6-tri-t-butyl-1,3,5-tri-

phosphabenzene, P3C3tBu3, afforded equimolar amounts of the lithium salt of the

five-membered 2,4,5-tri-tert-butyl-1,3-diphospholide anion, LiP2C3tBu3, and the

tricyclic compound 6-[phenyl(trimethylsilyl)amino]-3,5,7-tri-tert-butyl-1,2,4,6-tetra-

phosphatricyclo[3.2.0.0(2.7)]hept-3-ene.42 Metallation of the secondary phosphanes

{(Me3Si)2CH}(C6H4-2-NMe2)PH and {(Me3Si)2CH}(2-C5H4N)PH with nBuLi gave

the lithium phosphanides [{(Me3Si)2CH}(C6H4-2-NMe2)PLi(THF)2] and

[{(Me3Si)2CH}(2-C5H4N)PLi].43

A wide range of polyfunctional aryl and heteroaryl magnesium reagents have been

efficiently prepared by direct magnesiation with (TMP)2Mg � 2LiCl. Furthermore,

these compounds can serve as intermediates in natural product synthesis.44 The

reactions of MCl3 with Li2[PhB(NtBu)2] in 1:2 molar ratios produced the bisbora-

amidinates LiM[PhB(NtBu)2]2 (M= As, Sb, Bi).45 The reaction of bis(3,5-dimethyl-

pyrazol-1-yl)methane with nBuLi and several carbodiimide derivatives has enabled

the preparation of several new heteroscorpionate ligands in the form of the lithium

derivatives.46 Deprotonation of di(benzothiazol-2-yl)phosphine, HP(bth)2, afforded

the lithium phosphanide [(Et2O)2)Li(bth)2P] with both nitrogen atoms coordinated

to the lithium atom. This complex was employed in the synthesis of the hetero-

bimetallic complex [Li(bth)2P{Mn(CO)2Cp}2]n in which the phosphorus atom

bridges two Mn(CO)2Cp residues.47

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Group 16 donor ligands

A DGeq stability scale of secondary a-oxy-organolithium compounds has been

established from measurements of tin-lithium exchange equilibria in THF. A new

lead-lithium exchange equilibrium reaction was also reported.48 Lithium complexes

bearing dianionic amine bis(phenolate) ligands have been described. Reactions of

the ligand precursors Me2NCH2CH2N{CH2-2-HO-3,5-C6H2(tBu)2}2, (2-

C5H4N)CH2N{CH2-2-(HO)-3,5-C6H2(tBu)2}2 and MeOCH2CH2N{CH2-2-(HO)-

3,5-C6H2(tBu)2}2] with nBuLi afforded the dilithio species as tetra-nuclear com-

plexes, which showed excellent catalytic activities toward the ring-opening poly-

merisation of L-lactide in the presence of benzyl alcohol.49 The combination of

equimolar amounts of LiOAr and Mg(OAr)2 (OAr = aryloxide) has afforded

several lithium aryloxomagnesiates. Structural characterisation revealed several

discrete, solvent-separated species, including [Li(thf)4][Mg(BHT)3] �THF (BHT =

2,6-tBu2-4-MeC6H2O).50 An X-ray crystallographic study of an unusual lithium

silanolate hexamer, [LiO(SiMe2)OCH2SiMe3] has been described.51

3. Sodium

Dark-blue sodium nitride, Na3N, has been prepared by the reaction of metallic

sodium or liquid Na–K alloy with plasma-activated nitrogen at low pressure. The

compound crystallised in the cubic anti-ReO3-type structure according to powder

and single-crystal X-ray diffraction data.52 A unique 1-D chain of sodium clusters

containing Na6 rings and stabilised by a molybdenum-containing metalloligand has

been synthesised. DFT calculations revealed a resemblance in their aromatic

behaviour with the corresponding hydrocarbon analogues.53 A metallorganic gela-

tor formed from a mixture of a substituted nicotinic acid and its sodium salt has been

synthesised. The one-dimensional crystals were found to spontaneously gelify

dichloromethane and provide pyridine gels with high thermal resistance.54 The

structures of NaSCN, KSCN, RbSCN, and CsSCN complexes with 30,50-difluoro-

40-hydroxybenzyl-armed monoaza-15-crown-5 ether have been investigated. The Na

complex is a 1:1 polymer-like structure bridged by hydrogen bonding.55 Reaction of

zinc triflate with the lithium, sodium, and potassium salts of the bis(1,3-trimethyl-

silyl)allyl (A0) anion produced the fluxional triallylzincates Li[ZnA03], Na[ZnA03],

and K[ZnA03] rather than the initially expected neutral ZnA02.56 The reaction

between trimethylphosphine–borane and MeNa gave the polymeric complex

[{Me2P(BH3)CH2}Na(THF)]N.57 Reactions of the disodium salt of the 1,2-

bis[(2,6-diisopropylphenyl)imino]acenaphthene (Dipp-BIAN) ligand with one

equivalent of Me2AlCl produced [Na(Et2O)2(Dipp-BIAN)AlMe2], [Na(Z6-

C7H8)(Dipp-BIAN)AlMe2] and [Na(Z6-C6H6)(Dipp-BIAN)AlMe2]. The sodium

cation coordinates either one of the naphthalene rings or the diimine part of the

Dipp-BIAN ligand.58

The heavier alkali metal b-diketiminates [M{TbtNC(Me)CHC(Me)NMes}(THF)]

(Tbt = 2,4,6-[CH(SiMe3)2]C6H2; M=Na, K) have been prepared by the reaction of

the protonated ligand precursor, with MH (M = Na, K). Solvent-free

[M{TbtNC(Me)CHC(Me)NMes}] were prepared by the reaction of the Li derivative

with tBuOM (M = Na, K).32 Reaction of the sodium anion of (S)-N-(a-methyl-

benzyl)allylamine with t-butyl cinnamate resulted in a tandem aza–allyl conjugate

addition-Michael addition-ring closure reaction, to produce a chiral aminocyclo-

hexane containing six new vicinal stereogenic centres with excellent levels of

stereocontrol.59 Sodium and potassium salts of 1-methyl-3,5-diphenyl-4-

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methylamino-1,2,4-triaza-3,5-diborolyl have been prepared by deprotonation of the

ring nitrogen in the neutral precursor.60 The ring closure of 1,2-diisopropylhydrazine

and 1,1-bis(phenylchloroboryl)ethane produced a heterocyclic compound with a

CB2N2 framework. Deprotonation of this precursor yielded 1,2-diisopropyl-4-

methyl-3,5-diphenyl-1,2-diaza-3,5-diborolyl, a cyclopentadienyl analogue contain-

ing only one carbon atom in the ring skeleton. Lithium, sodium, and potassium salts

of the new ligand have been prepared and characterized.61

It has been discovered that simple hydridoalkylzincates(II) can be prepared from

mixtures of sodium and an excess of neat dialkylzinc reagent.62 The Na and K salts

of the [Zn(C5H5)3]� ion have been found to exhibit polymeric 1D and 2D structures,

respectively. In contrast, the dizincate [Na(THF)6][Zn2(C5H5)5] contains discrete

[Zn2(C5H5)5]� ions that consist of two {Zn(C5H5)2} groups with Z1,Z1 binding,

bridged by a C5H5 ring Z1-coordinated to each zinc atom.63 Twofold deprotonation

of benzene by a sodium monoalkyl bisamido manganate(II) reagent derived fromnBuNa, TMPH and Mn(CH2SiMe3)2 has produced the first inverse-crown complex

in which the transition-metal atoms are incorporated in the host. Variable-tempera-

ture magnetisation measurements showed that the complex was antiferromagnetic.64

The first sodium–magnesium and sodium–zinc ketimido complexes display contrast-

ing inverse crown ring and pseudo-cubane structures respectively. A sodium–zinc

heterotrianionic alkyl–alkoxide–amide adopts a third type of structure with a

stepped ladder motif.65 Two new inverse crown alkali–metal–zinc enolate com-

pounds have been prepared by reaction of the relevant mixed-metal base

[MZn(HMDS)3] (M = Na, K) with a stoichiometric amount of the sterically

demanding ketone 2,4,6-trimethylacetophenone.66 A series of polypyrazolylalumi-

nates [Na{AltBu2pz)4�xMex] (x = 3, 2, 1) have been prepared by treatment of

[NatBu2pz)] with varying equivalents of AlMe3.67 The lithium phosphanide

[{(Me3Si)2CH}(C6H4-2-NMe2)P]Li(THF)2] undergoes metathesis with MOtBu

(M = Na, K) to give the heavier alkali metal derivatives [{(Me3Si)2CH}(C6H4-2-

NMe2)P]M(TMEDA)].43

Reaction of the imidazolidine-bridged bis(phenol) [ONNO]H2 ([ONNO]H2 =

1,4-bis(2-hydroxy-3,5-di-tert-butylbenzyl)imidazolidine) with NaH provided {[ON-

NO]Na2(THF)2}2 � 2THF as a dimeric tetranuclear complex in an almost quantita-

tive yield.68 Mixed-metal alkoxide clusters of lanthanides and sodium

[Ln2Na8(OCH2CH2NMe2)12(OH)2] have been described as extremely active cata-

lysts for the ring-opening polymerisation of e-caprolactone and trimethylene carbo-

nate.69 From reactions between glycolide or lactide with 4-dimethylaminopyridine,

DMAP and NaBPh4 in benzene at 70 1C the cyclic ester adducts

(CH2C(O)O)6 �NaBPh4 and (CHMeC(O)O)6 �NaBPh4 were formed, respectively.

The mechanism for the formation of these 18-membered rings was discussed in terms

of an initial reaction between DMAP and NaBPh4 in hot benzene to produces NaPh

and DMAP: BPh3 in the presence of the monomer lactide.70 Reaction of the

polycyclic alumosiloxane [Ph2SiO]8[AlO(OH)]4 with either CpNa or with Me2Zn

produced [Ph2SiO]8[AlO2(Na)4 � 5(THF)] and [Ph2SiO]8[AlO(OH)]2[AlO2]2[Zn(OH)]2 � 2(OEt2), respectively.

71 The crystal structures of three hexameric double

heterocubane compounds containing NaOSiMePh2, each supported by THF and

[CpFe(CO)2]2 have been described.72 A series of sodium arylcyclotetrasiloxanolates

[4-RC6H4Si(O)ONa]4 and the corresponding (trimethylsiloxy)cyclotetrasiloxanes

[4-RC6H4Si(O)OSiMe3]4 (R = Cl, Br, CHQCH2, CH2Cl), have been prepared

as scaffolds for anchoring second order NLO active or fluorescent organic chromo-

phores.73 An organotin phosphonate oligomer composed of alternating

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heptanuclear tin phenylphosphonate and hexanuclear sodium phenylphosphonate

clusters has been synthesised by a debenzylation process under solvothermal

conditions.74 The synthesis and structure of two related sodium complexes has been

reported which demonstrate that sulfur can preferentially complex to sodium

irrespective of the presence of more apposite donor species such as DMF.75 Sodium

and potassium carbamotelluroates [M(R2NCOTe), M = Na, K, Rb, Cs] have been

synthesised in moderate to good yields by reacting carbamoyl chloride with the

corresponding alkali metal tellurides.76

4. Potassium, rubidium and caesium

Reaction of elemental caesium with 1,3-bis(trimethylsilyl)propene produced the

corresponding substituted allyl derivative. The complex and its previously prepared

potassium counterpart form the THF solvates K[1,3-(SiMe3)2C3H3](THF)3/2 and

Cs[1,3-(SiMe3)2C3H3](THF), respectively, which crystallise as coordination poly-

mers in the solid state.77 Desilylation of Me3SiCHPh2 with K, Rb and Cs alkoxides

produced the diphenylmethanides which exist as both contact molecules and

separated ion pairs.78 Reaction between the phosphine-borane adduct (Me3Si)2-

CHPPh2(BH3) and MeK gave [(Me3Si)2[Ph2P(BH3)}C]K, which was crystallised as

the PMDETA adduct.79 Reaction of the iron(II) complex of the 1:3 Schiff base

condensate of tris(2-aminoethyl)amine (tren) with 2-imidazolecarbaldehyde, H3L1,

[FeH3L1](ClO4)2), with MClO4 (M=K, Rb, Cs, and NH4) produced double salts of

the formula [FeH3L1](ClO4)2 �MClO4.80

Solvated potassium salts of the 9-BBN hydroborate anion have been prepared and

their structures have been determined by single-crystal X-ray diffraction analyses. A

tetrameric complex [LK[(m-H)2BC8H14]4 is formed when L is toluene.81 The am-

moniate [K17(Sb8)2(NH2)] � 17.5NH3, which contains crown-shaped [Sb8]8� Zintl

anions analogous to S8 rings, has been synthesised by reduction of antimony with

potassium in liquid ammonia.82 RbNH2 � 2/3NH3, has been synthesised from

rubidium hydride in liquid ammonia at �78 1C. The structure contains a three-

dimensional network of amide anions and ammonia molecules, which are inter-

connected via hydrogen bonds.83

The reaction of potassium hexamethyldisilazide (KHMDS) with the bulky

formamidine N(Diep)QC(H)NH(Diep) (Diep-FormH, Diep = 2,6-Et2C6H3) in

THF yielded the half deprotonated compound [K(DiepForm)(DiepFormH)], which

exhibited suppressed reactivity with the hexamethyldisilazide anion. Preparation in

the presence of the chelating solvents DME and PMDETA gave the fully deproto-

nated species [{K3(DiepForm)3(DME)3}n]3 and [{K(PMDETA)K(DiepForm)2}n].84

A solution of 1,3-(4-nitrophenyl)triazene in methanol treated with potassium

hydroxide yielded dark-red crystalline blocks of [{K(O2NC6H4NNNC6H4NO2)}2]n,

a triazenide complex polymer of potassium in which the centrosymmetric binuclear

entities are connected by weak intermolecular (KO)–O–� � � interactions.85 Similarly,

3-(4-carboxyphenyl)-1-methyltriazene N-oxide reacts with KOH in methanol/pyr-

idine to give [K{O2C-C6H4N(H)NN(CH3)O} � 4H2O]n.86 3-tert-butyl-5-methyl-1,2,4-

triazole has been reacted with KBH4 to give a new potassium tris(3-tert-butyl-5-

methyl-1,2,4-triazolyl)borate ligand.87 The solid-state structures of unsolvated potas-

sium, rubidium, and cesium carbazolates have been determined using X-ray powder

diffraction data. The potassium and rubidium carbazolates adopt a polymeric helical

arrangement, whereas caesium carbazolate forms a polymeric twisted column struc-

ture.88 A coordination polymer, [(Cs(bth)2P}8] (bth= benzothiazol-2-yl), was obtained

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when di(benzothiazol-2yl)phosphane was reacted with elemental caesium in a 1:1 ratio.

Each anion was coordinated to four caesium cations and vice versa.89

X-ray and neutron diffraction studies have shown that the controlled hydrolysis of

potassium 2-tert-butylphenoxide or 2-isopropylphenoxide leads to the encapsulation

of the water inside K6O6 hexameric drum aggregates through the formation of

strong hydrogen bonds and dative interactions between the host and guest.90 The

polysulfide [K2(THF)]S9 is accessible from reaction of S8 with [KSPPh2(BH3)], which

contains a S9-zigzag chain.91 The potassium salt of the anionic SPS pincer ligand

[K(THF)2][SPS(Me)] was isolated from reaction of the Li derivative with tBuOK.

Coordination of BH3 to the central phosphorus atom in [K(18-crown-

6)THF)][SPS(Me) �BH3] confirmed the phosphine character of the hypervalent

phosphorus atom.92 Potassium salts of chalcogenogermanate anions and their

corresponding hydrates have been prepared and crystallographically characterised.93

5. Beryllium

On the basis of quantum chemical calculations the multimetallocenes CpMnCp,

(M = Be, Mg, Ca, and Zn; n = 2–5) have been predicted to be thermodynamically

unstable with respect to loss of one metal atom except for the beryllium compounds,

which exhibit unusual stabilities in the gas phase for the whole series CpBenCp up to

n= 5.94 Beryllium has been successfully incorporated into a naphthalene-containing

Schiff base ligand. Evidence from 9Be and 1H NMR data and model compounds

indicated that the ligand completely encapsulates the beryllium cation via tetra-

dentate tetrahedral coordination using both phenol and imine donors.95 The binding

of beryllium to the iron transport protein transferrin has been found to proceed by

displacement of H+ from strong hydrogen bonds in the protein. This new view of

beryllium binding, in which beryllium behaves as a ‘‘tetrahedral proton’’, provides

insight into the transport mechanism of beryllium in chronic beryllium disease.96

The hexafluorodiberyllate (Ph4P)2[Be2F6] � 2CH3CN has been prepared by the reac-

tion of (Ph4P)2[Be2Cl6] with excess silver(I) fluoride in acetonitrile solution.97 (R,R)-

(N,N0)-diisopropylcyclohexyl-1,2-diamine reacts with equimolar amounts of BeCl2to give the donor acceptor complex ((R,R,S)-N,(S)-N)-[(C12H26N2)BeCl2]. The

reaction of this species with excess trimethylsilylazide led to the formation of the

corresponding azide.98 A Be phthalocyaninato(2�) complex with 4-picoline has been

obtained by recrystallisation of Be(II)Pc in 4-picoline under water-free conditions.99

Chloro-N0,N0-dimethylformamidinium (dimethylcyanamide)trichloroberyllate has

been prepared from BeCl2 and two equivalents of dimethylcyanamide.100 Single

crystals of [Be(OH2)4]Cl2 have been prepared by the reaction of thionyl chloride at

20 1C with HCl-containing, aqueous solutions of BeCl2.101

6. Magnesium

The reaction of boryllithium with 1 or 0.5 equivalents of MgBr2 has provided the

structurally characterised borylmagnesium bromide and bis(boryl)magnesium com-

plexes, 1 and 2. The reactivity of the borylmagnesium species with benzaldehyde was

different from that of the previously reported boryllithium.102 Single crystals of two

modifications of the new magnesium boride carbide MgB12C2, which conforms to

Wade’s Rules, have been synthesised from the elements.103 The crystal structure of

Mg(BH4)2 has been determined from synchrotron X-ray and neutron diffraction

data as a complex three-dimensional framework in which each Mg2+ ion is

tetrahedrally coordinated by four [BH4]� tetrahedra.104,105 A TMEDA complex of

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Mg(BH4)2 has also been structurally characterised.106 The solid-state reaction of

MgBr2, MgBr2(Et2O) or MgBr2(Me2O)1.5 and NaB3H8 has afforded Mg(B3H8)2 and

the crystalline ether adducts respectively.107 The single-source precursors

[Mg(C3H6BC8H14)2] and [Mg{C3H6B(C6H11)2}2] have been applied in chemical

vapour deposition processes. Deposition procedures in a temperature range from

500 to 1000 1C produced smooth and thin films with Mg and B in the ratio 1:2.108

Group 14 donors

Bis(mesityl)magnesium has been established as an accessible, practical, convenient,

and non-nucleophilic carbon-centred base for efficient access to silyl enol ethers from

a series of ketone substrates.109 The reaction between either MgI2 or CaI2 and 2

equivalents of [(Me3Si)2{Me2(H3B)P}C]K provided the corresponding organo-alka-

line earth metal compounds [(Me3Si)2{Me2(H3B)P}C]2M in moderate to good

yields.110 Sequential addition of iPrMgCl and nBuLi to sp3 hybridised iodoalcohols

has been described. Interception of the resulting cyclic Grignard reagents with a

slight excess of an electrophile resulted in a diverse range of substituted alcohols.111

Group 15 donors

Reduction of two magnesium(II) iodide complexes with potassium metal in toluene

has provided the first thermally stable magnesium(I) compounds, LMgMgL (where

L is [DippNC(NiPr2)N(Dipp)]� or [{DippNC(Me)}2CH}]�, 3, in moderate yields.

The results of X-ray crystallographic and theoretical studies were consistent with

central Mg22+ units that have single, covalent magnesium–magnesium bonding

interactions with 2.8508(12) and 2.8457(8) A bond lengths, respectively, and

predominantly ionic interactions with the anionic ligands.112

A wide range of polyfunctional aryl and heteroaryl zinc reagents have been prepared

by direct zincation using (TMP)2Zn � 2MgCl2 � 2LiCl as an exceptionally active

base.113 A range of polyfunctionalised quinolines have been prepared via chemo-

and regio-selective magnesiation reactions using Mg reagents, such as iPrMgCl �LiCland TMP2Mg � 2LiCl.114 It has been reported that benzene can be easily 1,4-

dideprotonated on reaction with two equivalents of a synergic mixture of (tBu2Zn),

NaTMP and TMEDA to give a unique 1,4-dizincated benzene product which has

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been characterised by X-ray crystallography.115 Several magnesium compounds

including [(dioxane)MgPh2]N and (THF)2Mg(NPh2)2 have been reported to tetra-

coordinate species.116,117 The transamination reaction of Mg[N(SiMe3)2]2 with (2-

pyridylmethyl)(tert-butyldimethylsilyl)amine yielded the corresponding homoleptic

magnesium bis[(2-pyridylmethyl)(tert-butyldimethylsilyl)amide].118 Magnesium and

zinc complexes of the monoanionic ligands N,N0-bis(2,6-diisopropylphenyl)triaze-

nide, N,N0-bis(2,6-diisopropylphenyl)acetamidinate and N,N0-bis(2,6-diisopropyl-

phenyl)(tert-butylamidinate) have been synthesised.119 Metallation of N-

(diphenylphosphanyl)-2-pyridylmethylamine with nBu2Mg resulted in the formation

of the magnesium bis[N-(diphenylphosphanyl)-2-pyridylmethylamide].120 The al-

kane elimination reaction between nBu2Mg and excess 3,5-diisopropylpyrazole

(iPr2PzH) has afforded the dinuclear magnesium pyrazolate [{Mg(iPr2P-

z)2(iPr2PzH)}2].

121 Reactions of {(tBuHN)3PNSiMe3 with nBu2Mg has yielded the

monodeprotonated complex [Mg{(NtBu)(NSiMe3)P(NHBu)2}2].122 The unusual

Mg4N4 cubane imide complexes [(ArNMg � dioxane)4 � 3(dioxane)] and

[(ArNMg �THF)4] (Ar = 2,4,6-Cl3C6H2) have been prepared by the equimolar

reaction of nBu2Mg with the primary amine.123 The coordination chemistry bis-[2-

(3,5-dimethyl-1-pyrazolyl)ethyl]amine (LH) with nBu2Mg and monoalkyl magne-

sium halides has been studied. Reaction of 2 equivalents of LH with nBu2Mg gave

the bis(amido) complex [L]2Mg while reactions with iPrMgCl and MeMgI afforded

the corresponding halide complexes.124 The reaction of 5-iodouracil with MeMgCl

followed by the addition of iPrMgCl �LiCl, has provided the corresponding trimag-

nesiated species, which reacts with various electrophiles to give selectively 5-

functionalized uracil derivatives.125 The mechanism for CO2 fixation by alkylmag-

nesium amides and magnesium bisamides has been analyzed on the basis by DFT

methods.126 The redox properties of the phthalocyanine-like tetrakis(thiadiazole)-

porphyrazine, [TTDPzMg], have been investigated by cyclic voltammetry and

density functional theory.127

Group 16 donors

A rare example of a structurally characterised magnesium alkyl alkoxide with an

Mg4O4 cubane structure, [Mg(CH2SiMe3)(m3-OCH2SiMe3)]4, has been identified as

the product of oxidation of ClMgCH2SiMe3 with traces of O2.128 Magnesium

complexes containing ketiminate ligands have been synthesized. nBu2Mg reacted

readily with two equivalents of [MeC(O)CHC(NHAr)Me] (Ar = 2,6-diisopropyl-

phenyl), to generate [MeC(O)CHC(NAr)Me]2Mg.129 Magnesium alkoxides have

been reported to undergo a hydride-transfer oxidation with benzaldehyde as the

oxidant. This magnesium variant of the Oppenauer oxidation has been used for the

synthesis of polyfunctional biaryl ketones.130 The magnesiation of halogenated

aromatic and heteroaromatic carboxylic acids has been accomplished by their

treatment with MeMgCl and subsequent reaction with iPrMgCl �LiCl. The resultingdouble-magnesiated species reacted with a variety of electrophiles in up to 97%

yield.131

7. Calcium, strontium and barium

Ca(NH2BH3)2 releases hydrogen over a temperature range of 100 to 170 1C without

foaming and has been described as a potential H2-storage material.132 The alkaline

earth tricyanomethanides Mg(tcm)2 � 2H2O, Ca(tcm)2, Sr(tcm)2 �H2O and

Ba(tcm)2 � 2H2O have been prepared from aqueous solutions of the respective

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chlorides and solid silver tricyanomethanide.133 A series of trifluoroacetic acid

(H-TFA) derivatives of the heavier alkaline earths have been synthesised though

the dissolution of the alkaline earth metal in H-TFA.134

Although a monomeric calcium ‘carbene’ complex, [(2,6-iPr2C6H3NPPh2)2CCa],

has been reported to display sluggish reactivity toward unsaturated electrophiles, it

did act as catalyst for the oligomerisation of isocyanates.135 A related barium

complex, [(2,6-iPr2C6H3NPPh2)2CBa(THF)3], has also been described.136 A diaryl

calcium compound has also been isolated for the first time by fractionated crystal-

lization of mesitylcalcium iodide. Bis(2,4,6-trimethylphenyl)calcium and Tris(2,6-

dimethoxyphenyl)dicalcium iodide showed extremely high solubilities in THF even

at �90 1C.137 In related work, the transmetalation of phenylcopper and Ca metal

yielded the solvent-separated cuprate [(THF)3Ca(m-Ph)3Ca(THF)3]+[Ph–Cu–

Ph]�.138 Sterically hindered Lewis base free bis(1,2,4-tri-tert-butylcyclopentadienyl)-

strontium and bis(1,2,4-tri-tert-butylcyclopentadienyl)barium have been synthesised

and are suitable precursors for atomic layer deposition of thin films.139 Benzylcal-

cium complexes with modified fluorenyl ligands have been prepared and utilised as

initiators for syndiotactic styrene polymerisation.140

The structures of (DME)2Ca(NPh2)2, (THF)4Sr(NPh2)2 and (THF)4Ba(NPh2)2have been reported,116 as have a variety of routes to the closely related phenyl-

amides.117 Several diphenylphosphides including (THF)4Ca(PPh2)2 have also been

described.141,142 The diisopropylpyrazoloate [{Ca(iPr2Pz)2(iPr2PzH)2}2] has been

obtained as the product of redox-transmetallation/ligand-exchange reaction between

an excess of the metal, 2 equivalents of iPr2PzH, and Hg(C6F5)2. A similar reaction

with Sr metal led to the isolation of [Hg3(iPr2Pz)4(C6F5)2] while direct metallation of

barium with iPr2PzH afforded [{(Ba(iPr2Pz)2(py)3}2] upon treatment with pyri-

dine.121 A variety of new calcium b-diketiminate derivatives have been described

including simple amide and cyanide complexes.143 The reaction of a b-diketiminate-

stabilised calcium diphenylamide with the dialkylborane 9-BBN has allowed the

synthesis of a calcium borohydride along with an amidoborane reaction coproduct

via a likely sigma-bond metathesis mechanism.144 This compound was also included

in a broad study of the reactivity of the hydrocarbon–soluble calcium hydride

complex [{CH{(MeC)(DippN)}2}CaH(THF)}2] with a variety of substrates. Addi-

tion of this hydride to CQO and CQN functionalities gave easy access to calcium

alkoxide and amide complexes and addition to epoxides resulted in nucleophilic

ring-opening reactivity.145 A hydrocarbon–soluble dimeric calcium monofluoride,

[{CH{(MeC)(DippN)}2}CaF(THF)}2], 4, has been reported as a precursor for the

preparation of thin layers of transparent CaF2 at room temperature by dip-coat-

ing.146 A closely related fluoride complex, 5, has been reported as an intermediate in

the C–F cleavage decomposition of an unusual calcium b-diketiminate complex, 6,

which exhibits an unprecedented binding mode of a CF3 group.147

It has been reported that the azametallacyclopropane complex Ca(Z2-

Ph2CNPh)(HMPA)3 can be conveniently obtained via a one-pot procedure. Its

catalytic activity has been assayed in a variety of reactions.148 The b-diketiminato

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[{CH{(MeC)(DippN)}2}Ca{N(SiMe3)2}(THF)] effects intermolecular hydropho-

sphination of a range of alkenes and alkynes. In behaviour reminiscent of lantha-

nocene(III) catalysis, a more electrophilic alkene was polymerised to phosphine-

terminated macromolecules.149 The mononuclear complex [{iPr2ATI}Ca-

{N(SiMe3)2}(THF)2] [iPr2ATI = N-isopropyl-2-(isopropylamino)troponiminate]

has been reported to display a high reactivity as a catalyst in the intramolecular

hydroamination/cyclisation reaction of nonactivated aminoalkenes.150 The synthesis

and structural characterization of an unusual trinuclear barium aminebis(phenolate)

complex has been described reported along with its application as an initiator for the

ring-opening polymerisation of e-caprolactone and L-lactide.151

A new class of heterobimetallic Group 1/Ba compound, e.g. [Li2(thf)2-

{Ba(Odpp)4}] (HOdpp = 2,6-diphenylphenol), which display significant metal–

arene interactions, has been reported.152 Inspired by the active site of Photosys-

tem-II, the cubane complex [Mn4Ca2Cl4(m-OCH2CH2OMe)8] has been described, in

which the calcium atoms result in a flattening of the Mn4 unit.153 Reaction between

BaI2 and NaOCH(CF3)2 in a 1:1 stoichiometry gave the heterometallic compound

NaBaI2(OCH(CF3)2)(H2O)(THF)0.5 which redistributed upon attempted crystal-

lisation.154 The products of reactions between the trifluoroacetates [Y(TFA)3-

(H2O)3], [Cu(TFA)2(MeOH)] and [Ba(TFA)2]N in the presence of excess N-

methyl-diethanolamine have been used as precursors for high Tc superconduc-

tors.155 Several dianionic bis beta-ketoesterates of barium, strontium and calcium

have been synthesised and studied as CVD precursors.156 Two complexes of calcium

croconate Ca(m3-C5O5)(H2O)3 and calcium oxalato-croconate Ca2(m4-C5O5)(m6-C2O4)(H2O) have been synthesised by soft chemical routes.157 Direct treatment of

2,6-dibenzylphenol (HOdbP) with strontium or barium metal in the absence of

solvent at high temperature has provided the corresponding phenolates Sr(OdbP)2and Ba(OdbP)2. Recrystallisation of Ba(OdbP)2 from THF gave a good yield of the

crystalline dimer [Ba(OdbP)2(THF)]2 � 2THF.158 The adducted salicylate com-

pounds, [Ca(SAL)2(phen)]n, [Sr2(SAL)4(phen)4] and (Ba(SAL)2(phen)2]n (SAL =

salicylate) have been obtained by the addition of 1,10-phenanthroline (phen) to the

corresponding base-free compounds.159

Ligand/reagent abbreviations

BHT 2,6-Di-tert-butyl-4-methylphenol

bth Benzothiazole

Cy Cyclohexyl

Diep 2,6-Diethylphenyl

Dipp 2,6-Diisopropylphenyl

Dippbian 1,2-Bis[(2,6-diisopropylphenyl)imino]acenaphthene

DFT Density functional theory

Dipp 2,6-Diisopropylphenyl

DME Dimethoxoethane

HMDS Hexamethyldisilazide

HMPA Hexamethylphosphoramide

HOdbP 2,6-Dibenzylphenol

hppH 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidine

LDA Lithium diisoproylamide

Liq Lithium 8-hydroxyquinolate

Mes 2,4,6-Trimethylphenyl

PMDETA Pentamethyldiethylenetriamine

py Pyridyl

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Pz Pyrazol-1-yl

SAL Salicylate

TFA Trifluoroacetate

thd 2,2,6,6-Tetramethylheptanedionate

THF Tetrahydrofuran

TMCDA Trans-N,N,N0,N0-tetramethylcyclohexanediamine

TMEDA N,N,N0,N0-Tetramethylethylenediamine

TMP 2,2,6,6-Tetramethylpiperidide

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