Organometallic chemistry volume38

Specialist Periodical Reports Edited by Ian J S Fairlamb and Jason M Lynam Organometallic Chemistry Volume 38 Organometallic Chemistry Volume 38 A Specialist Periodical Report Organometallic Chemistry Volume 38 A Review of the Recent Literature Editors I Fairlamb and J Lynam, University of York, UK Authors Rory L Arrowsmith, University of Bath, UK M.P Cifuentes, Australian National University, Canberra, Australia Sarah B.J Dane, University of Cambridge, UK Philip J Harford, University of Cambridge, UK L.J Higham, Newcastle University, UK M.G Humphrey, Australian National University, Canberra, Australia Anant R Kapdi, Institute of Chemical Technology, Mumbai, India Timothy C King, University of Cambridge, UK Sofia I Pascu, University of Bath, UK Hubert Smugowski, University of Bath, UK A.E.H Wheatley, University of Cambridge, UK D.S Wright, University of Cambridge, UK If you buy this title on standing order, you will be given FREE access to the chapters online Please contact sales@rsc.org with proof of purchase to arrange access to be set up Thank you ISBN 978-1-84973-376-2 ISSN 0301-0074 DOI 10.1039/9781849734868 A catalogue record for this book is available from the British Library r The Royal Society of Chemistry 2012 All rights reserved Apart from fair dealing for the purposes of research or private study for non-commercial purposes, or for private study, criticism or review, as permitted under the Copyright, Designs and Patents Act, 1988 and the Copyright and Related Rights Regulations 2003, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reproduction in accordance with the terms of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 0WF, UK Registered Charity Number 207890 For further information see our web site at www.rsc.org Preface Ian J S Fairlamb and Jason M Lynam DOI: 10.1039/9781849734868-FP005 The format for this Volume follows on from recent publication in this series with two types of contributions: Critical reviews and comprehensive reviews The critical reviews in this Volume discuss both fundamental aspects of organometallic chemistry and also its interface with other fields of study Rory Arrowsmith, Sofia Pascu and Hubert Smugowski discuss how metal complexes may be applied to biomedical chemistry with a view to developing novel imaging agents Building on a report in Volume 37, Lee Higham describes investigations into how the air-stability of primary phosphine ligands may be predicted using a combination of experimental and theoretical studies Anant Kapdi has reviewed the application of metal catalyst systems in C–H bond and C–X activation processes, particularly aligned with organic chemistry Comprehensive reviews of the organometallic chemistry in this Volume detail the literature published in 2010 on the chemistry of metal clusters written by Mark Humphrey and Marie Cifuentes, the chemistry of the alkali and coinage metals by Philip Harford and Andrew Wheatley as well as recent developments in Group (Be-Ba) and Group 12 (Zn-Hg) compounds by Sarah Dane, Timothy King and Dominic Wright This Volume therefore covers many synthetic and applied aspects of modern organometallic chemistry from various areas of the periodic table Department of Chemistry, University of York, York YO51 5DD, UK E-mail: ijsf1@york.ac.uk; jason.lynam@york.ac.uk Organomet Chem., 2012, 38, v–v | v  c The Royal Society of Chemistry 2012 CONTENTS Cover Ball and stick representation of Grubbs generation II catalyst Preface Ian J S Fairlamb and Jason M Lynam v New developments in the biomedical chemistry of metal complexes: from small molecules to nanotheranostic design Rory L Arrowsmith, Sofia I Pascu and Hubert Smugowski Introduction Summary Acknowledgements Authors References Air-stable chiral primary phosphines part (ii) predicting the air-stability of phosphines Beverly Stewart, Anthony Harriman and Lee J Higham Introduction Conclusions References 26 26 26 27 36 36 45 45 Organomet Chem., 2012, 38, vii–viii | vii  c The Royal Society of Chemistry 2012 Organometallics aspects of C–H bond activation/functionalization Anant R Kapdi Introduction Historical background Electrophilic aromatic substitution (SEAr mechanism) Oxidative addition mechanism Concerted metalation deprotonation (CMD) (s-bond metathesis of C–H bond) Summary References 48 48 50 51 58 63 67 67 Organo-transition metal cluster complexes 75 Mark G Humphrey and Marie P Cifuentes Introduction Theory Medium and high-nuclearity clusters Group Group Group Group 10 Group 11 Mixed-metal clusters Abbreviations References 75 75 76 77 77 82 82 83 83 88 89 Alkali/coinage metals – organolithium, organocuprate chemistry Philip J Harford and Andrew E H Wheatley The alkali metals Group 11 metals Abbreviations References 91 96 106 108 Group (Be–Ba) and group 12 (Zn–Hg) 112 Sarah B J Dane, Timothy C King and Dominic S Wright Scope and organisation of the review References 112 123 viii | Organomet Chem., 2012, 38, vii–viii 91 Abbreviations Ac acac acacen Ad AIBN ampy Ar Ar* Ar f arphos ATP Azb 9-BBN BHT Biim BINAP bipy Bis bma BNCT Bp bpcd bpk Bpz4 But2bpy t-bupy Bz Bzac cbd 1,5,9-cdt chd chpt CIDNP [Co] (Co) cod coe cot CP/MAS Cp CpR acetate acetylacetonate N,N -ethylenebis(acetylacetone iminate) adamantyl azoisobutyronitrile 2-amino-6-methylpyridine aryl 2,4,6-tri(tert-butyl)phenyl 3,5-bis(trifluoromethyl)phenyl 1-(diphenylphosphino)-2-(diphenylarsino)ethane adenosine triphosphate azobenzene 9-borabicyclo[3.3.1]nonane 2,6-dibutyl-4-methylphenyl biimidazole 2,2 -bis(diphenylphosphino)-1,1 -binaphthyl 2,2 -bipyridyl bis(trimethylsilyl)methyl 2,3-bis(diphenylphosphino)maleic anhydride boron neutron capture therapy biphenyl 4,5-bis(diphenylphosphino)cyclopent-4-ene-1,3-dione benzophenone ketyl (diphenylketyl) tetra(1-pyrazolyl)borate 4,4 -di-tert-butyl-2,2 -bipyridine tert-butylpyridine benzyl benzoylacetonate cyclobutadiene cyclododeca-1,5,9-triene cyclohexadiene cycloheptatriene chemically induced dynamic nuclear polarisation cobalamin cobaloxime [Co(dmg)2 derivative] cycloocta-1,5-diene cyclooctene cyclooctatriene cross polarisation/magnetic angle spinning Z5-cyclopentadienyl Z5-alkylcyclopentadienyl Organomet Chem., 2012, 38, ix–xiii | ix  c The Royal Society of Chemistry 2012 dipp Ph N Ph dipp Mg N N N Me Me Mg R N n Me nBu Cl N dipp Mg N Cl Bu N Me dipp Fig Structure of hydrid scorpionate complex and N-heterocyclic carbine complex R Mg R R Mg Mg R O Mg R O Mg O R O O O O Mg O R R Mg R 10 Fig Structure of the first bis-cubane complexes 10 lactides Also worthy of mention is the first example of an N-heterocyclic carbene complex of a Grignard reagent (Fig 1).15 The applications of s-bonded organomagnesium compounds as singlesource precursors for the deposition of MgO and Li-containing MgO is another interesting development.18,19 The organomagnesium cubanes [MeMg(m3-OR)]4 (R=iPr, tBu, Cy) (8) and the first examples of bis-cubanes [Me6Mg7(m3-OR)8] (R=Et, nPr, nBu)] (9) (Fig 2) show decomposition in the solid state at relatively low temperatures into MgO nanoparticles, while the heterometallic Mg/Li cubanes [Li(thf)(MeMg)3(m3-OR)4] (10) give Li-containing MgO nanoparticles This type of bottom-up approach shows considerable promise for the future Comparatively few r-bonded organometallics of the other group metals were reported in 2010.20–27 An important example of an organoberyllium complex is that of mononuclear [Be{1,3-(Me3Si)2C3H3}2.Et2O] (11) (Fig 3) whose structural characterization provides the first authentication of a s-bound allyl beryllium complex 11 is fluxional in solution, involving low-energy interchange between Z1- and Z3-allyl ligand bonding.20 In addition to this process, the first spectroscopic evidence using 9Be NMR spectroscopy of a Schlenk-type equilibrium for an organoberyllium complex was also obtained DFT calculations suggest that p-allyl bonding is energetically favourable in the absence of coordinated bases 114 | Organomet Chem., 2012, 38, 112–127 OEt2 Me3Si SiMe3 Be SiMe3 SiMe3 Fig Structure of the monomer 11 CH(SIMe3)2 CH(SiMe3)2 [M{CH(SiMe3)2}2(thf)n] N Dipp N N M = Mg-Ba N Dipp Dipp N M N + N Dipp N Dipp M N -CH2(SiMe3)2 Dipp N M N -CH2(SiMe3)2 N Dipp CH(SiMe3)2 Dipp CH(SiMe3)2 CH(SiMe3)2 12 N Dipp N M N Dipp (thf)n 13 Scheme One of the developing themes in this area is the investigation of the reactivity patterns of the organometallics of the heavier group metals (Ca–Ba) and the ways in which these parallel or are different from far more well studied organomagnesium reagents.21–26 One such study has shown that calcium alkyls or amides react with triphenylphosphine oxide (Ph3PO) or diphenyl phosphine oxide (Ph2P(H)O) in the presence of PhSiH3 to give PIII reduction products (specifically the Ph2POÀ anion), via a combination of deprotonation and C–P bond cleavage, as well as P–P bonded products.21 A further report has uncovered the unexpected reactivity of a bis-imino-pyridine ligand framework (12) with heavier Group organometallics (Scheme 3).22 The common sequence of these reactions involves the de-aromatisation of the pyridyl ring unit in the initial step followed by intra- and inter-molecular deprotonation of the Me groups within the bis-imino-pyridine ligand The tendency for de-aromatisation vs C–H methyl-deprotonation is dependent on the Group metal employed Structurally-characterised representatives of the final deprotonated products 13 are of some interest Whereas the bis-thf solvated complexes of Mg and Ca are mononuclear, the unsolvated Sr and Ba complexes form six-fold symmetric macrocycles in which the monomer units are linked by long-range intermolecular C M interactions (Fig 4) A further interesting example of the non-innocence of a ‘spectator’ ligand is seen in the interaction of Et3Al with the b-diketiminato calcium amide [{DippN C(Me) CH C(Me) NDipp}Ca{N(SiMe3)2}(OEt2)] (14) (Scheme 4), the product of the reaction being the complexes 15a and 15b (differing only in the number of metal-bridging Et groups in their [Et4Al]À anions).26 Organomet Chem., 2012, 38, 112–127 | 115 N N M N N N N N M M N N N N M M N N N N N M N N Fig Six-fold symmetric structures of the Sr and Ba complexes 13 (n=0) Me Me Et Al N Dipp 2Et3Al N Ca Ca Dipp N(SiMe3)2 Et2O Et Dipp Me Me N Al Et Dipp Me Al Et N + Et Ca Al Et N N Dipp Me 14 Et 15a Dipp Me 15b Scheme Some of the most interesting structural studies in 2010 were on Group organometallics p-complex.4,28–33 Developments in the chemistry of Mg–Mg bonded, MgI compound [{{N(Dipp) C(Me)}2CH}MgMg{{N(Dipp) C(Me)}2CH}] (16) are particularly noteworthy 16 reduces benzophenone and anthracene to give thermally-stable magnesium ketyl and magnesium anthracene complexes, 17 and 18 respectively (Scheme 5).28 Further structural and synthetic studies of the monomeric [Sr{1,3(Me3Si)2C3H3}2 Á (thf)2] (19) and polymeric [Ba2{1,3-(Me3Si)2C3H3}5 Á K Á thf] (20) complexes of Sr and Ba show that p-bonding is indeed adopted for the heavier Group metals using this allyl ligand (cf the s-bonding of the same allyl ligand in 11, Fig 3).29 Inter-30 and intra-molecular31 neutral p-arene metal interactions have also been seen in recent studies A particularly interesting one being the structural study of the benzene solvate [{Ba(GaCl4)2}3(C6H6)2] (21) which is found to contain two distinctly dierent Ba2 ỵ environments in the solid state.30 While one Ba2 ỵ site is surrounded by twelve Cl-atoms in an icosahedral geometry, the other consists of a [Ba(Z6-C6H6)2]2 þ sandwich in which the Ba2 þ ion is further coordinated equatorially by six Cl- atoms (Fig 5) p-Arenes (albeit with anionic arene groups) also form the basis for the structure of the unusual Normant-type cuprate [ICa(m-Z1,Z6-Mes2Cu)]4 (22).33 116 | Organomet Chem., 2012, 38, 112–127 Scheme (a) (b) Cl Cl Ba Cl Cl Cl Cl 21 22 Fig a) The sandwich arrangement found in the solid-state structure of 21 and b) the metallocyclic structure of the cuprate 22 Group 12 Fundamental structural studies of simple organozinc compounds of the types RZnX or R2Zn were rare in 2010.34–36 Most commonly solid-state structural investigations concerned compounds of the type [LZnR]n in which a very broad range of ligand types or atoms (L) were present Particular families of organometallic compounds that were investigated include new heterometallic s-block/zinc bases for selective deprotonation of organic and inorganic substrates,37–42 nitrogen-based ligands (tris-pyrazolyl ligands,43–45 hydrazides,46a–47 b-ketiminates48–51 and related guanidate, amidinate,52–54 other chelating N-centred organic anions,11,55–61 and P-N Organomet Chem., 2012, 38, 112–127 | 117 framework ligands6,62–67), oxo-compounds,68,69 alkoxides,70–78 hydrides,79,80 and heterometallic cages.81 One of the continuing highlights in this field has been the development of synergic heterometallic bases The type of selectivity which typifies the reactions of these species with organic molecules is well illustrated by reaction of the heterometallic zinc reagent [(tmeda)Na(mtmp)(m-tBu)Zn(tBu)] (23) with benzyl-methyl-ether (24) which gives exclusively [(tmeda)Na(m-tmp)(m-C6H4CH2OMe)Zn(tBu)] (25), containing only the ortho-metallated aromatic ligand (Scheme 6).37 This is completely unlike reactions involving simple bases like nBuLi or tBuLi alone which deprotonate 24 at the more thermodynamically-favourable benzylic CH2group A further remarkable example of the synthetic potential and extreme basicity of this type of mixed-metal reagent is found in the case of the reaction of the ethylene diamine [{iPrN(H)CH2CH2N(H)iPr}] (26) with a 1:1 mixture of ZnR2 (R¼Me or tBu) and tBuLi which results not only in deprotonation of the N-H groups but also in formal loss of H2 within the -CH2–CH2- bridge in the product complex 27 (Scheme 7).39 This latter transformation actually involves hydridic intermediates, as illustrated by the formation of the alkoxide anion [tBu2C(H)–O]À upon addition of t Bu2C¼O to the reaction mixture OMe 24 N N N N Zn Na t Bu Zn Na N N t Bu MeO 23 25 Scheme i Pr N Zn H N i i N H Pr Pr R2Zn / tBuLi tmeda N i Pr Li N 26 N 27 Scheme 118 | Organomet Chem., 2012, 38, 112–127 R t Bu Some of the most interesting studies in the area of s-bonded organometallics containing N- or O-centred ligand sets have concerned applications in materials, polymer- and small-molecule catalysis and H2-storage A general shift from pure structural interest towards the applications and novel reactivity is a clear trend in the most recent literature A case in point is a study of the effects on H2 uptake brought about by introducing fluorinated aryl substituents into hydrazide cages.46a It is found that a large (ten-fold) increase in H2 uptake occurs when the R and R -groups are switched from alkyl to C6F5 groups in cages like 28 (Fig 6a) This result has potentially far-reaching implications to a range of H2-storage metal-organic frameworks like MOF-546b since it strongly suggests that the inorganic nodes in such systems rather than the linkers are the main site of H2-uptake A further report that ZnEt2, MgBu2, and nBuLi can act as excellent precatalysts for the catalytic addition of amines to carbodiimides is also worthy of mention in this context.52 The structurally-characterised dimeric zinc guanidinate complex [Zn(Et){(4-tBuC6H4)-N¼C(N-iPr)(NH-iPr)}]2 (29) was shown to act as an efficient catalyst in the guanylation reaction, suggesting a mechanism involving the formation of amido intermediates (Fig 6b) Interesting new developments employing diorganozinc reagents in the catalytic reduction of ketones to alcohols in the presence of silanes [R3SiH] also constitute an important advance in the area of the chemistry of s-bonded organozinc chemistry.71 The catalytic reduction of a range of ketones in the presence of ca mol% ZnEt2/ArOH occurs with turnover numbers of up to 1000 hr À Although the mechanism of this reaction is currently not known structural studies indicate the key importance of zinc alkoxide intermediates In a separate study of a similar catalytic reduction system, involving organozinc/silane catalysts, zinc hydrides have also been shown to be involved.79 The non-innocent behaviour of the bis(phosphinimino)methanide ligand [CH{P(R2)¼NR }2]À provides an interesting way by which new and facile approach to new tripodal ligand systems.62,65 A novel example of this characteristic was recently illustrated by the reactions of [CH{P(Ph2)¼NSiMe3}2ZnR] [R¼N(SiMe3)2 (29a), Ph (29b)] with BH3 Á thf.62 In the case of 29b (a) (b) R′ R′ N R N Zn Zn HN N R' R H N H N Zn Zn R N R′ NH R 28 Fig a) Structure of 28 and b) proposed mechanism of catalytic addition of amines to give carbodiimides Organomet Chem., 2012, 38, 112–127 | 119 this leads to the formation of the novel complex [(BH3)CH{P(Ph2)¼NSi Me3}2ZnR] (30) in which the Zn2 ỵ ion is involved in a B–H Zn interaction with the assembled ligand framework (Scheme 8) One of the structural highlights of 2010 was a report of the first zinc alkoxide trimer.70 Placing the dimeric thf solvate [tBuZnOtBu Á thf]2 (31) under vacuum at slightly elevated temperature followed by crystallization of the solid residue gave the trimer [tBuZnOtBu]3 (32), whose solid-state structure can be viewed as a dimeric Zn2O2 unit that is further coordinated by a [tBuZnOtBu] monomer (Scheme 9) Interestingly, the expected tetramer [tBuZnOtBu]4 (33) is obtained from the direct reaction of tBu2Zn with t BuOH in toluene The tetramer 33 is also obtained by grinding the trimer 32 with a glass rod, providing a unique example of a mechanochemical transformation in this area and suggesting that the trimer is a metastable form of the zinc alkoxide Further calculations have confirmed that the conversion of 32 into 33 is exothermic and exogenic.82 Also of interest structurally and in terms of reactivity is a report of the C–H bond activation of the Me-groups of ZnMe2 in the reaction with the triply-bonded [(RO)3MoMo(OR)3] (34).81 The MoRMo bond is maintained in these reactions, an example being complex 35 which is formed at room temperature with excess ZnMe2 (Scheme 10) Further calculations and gas-phase studies concerning s-bonded organozinc compounds have also made significant advances in this area.82–86 Among these is the characterization of methylzinc hydride [HZnCH3] (36) in the gas-phase.83 It was shown to have a monomeric structure by highresolution spectroscopic techniques The molecule was synthesized by two methods: the reaction of dimethylzinc with a mixture of hydrogen gas and methane in an AC discharge and the reaction of zinc vapor with methane in a DC discharge The electric quadrupole moment determined Scheme t Bu t Bu Zn Bu t Bu Zn vacuum Bu O thf +35 °C Bu O Zn t Bu O t Bu 31 Zn t t O Zn t Bu Bu O thf t t t Zn grinding Bu Zn O Bu Bu Scheme 120 | Organomet Chem., 2012, 38, 112–127 t Bu t t 32 Zn O Bu Bu t Bu Zn O t t O 33 t Bu Cy Zn O (CyO)3Mo Mo(OCy)3 Mo Zn Cy RT 34 O Zn Cy Cy O Zn H2 C O xs ZnMe2 H2 C Zn Mo CH2 O O Zn Cy Cy 35 Scheme 10 Dipp N N Dipp N Ga N I Cd N Cd N Dipp I Ga N N Dipp 37 Fig Structure of the first Cd–Ga bonded complex 37 for [H67ZnCH3] suggests covalent bonding at the zinc nucleus, consistent with theoretical predictions In contrast to s-bonded organozinc compounds, very few structural and theoretical studies in 2010 focused on their r-bonded organocadmium counterparts.51,87,88 Although not strictly speaking organometallic (in that they not contain C-metal bonds) complexes of the anionic gallium(I) heterocycle [:Ga(DAB)]À (DAB={N(Dip)C(H)}2, Dipp=2,6-iPr2C6H3) are worth mentioning here, particularly the Cd dimer [(DAB)GaCd(tmeda)(m-I)]2 (37) (Fig 7) which contains the first example of a Cd–Ga bond [2.509(1)–2.5479(9)A˚].88 The structural characterisation of p-complexes of zinc and cadmium continues to provide many fascinating new results.89–92 Three recent examples are shown in Fig The cluster compound 38 (Fig 8) is obtained by the reaction of ZnMe2 with [Cp*Rh(GaCp*)2(GaCl2Cp*)] (39) and contains 18-electron square-pyramidal Cp*RhZn4 building units which result from a combination of Ga/Zn, Me/Cp* and Me/Cl exchange.90 It has an interesting dimeric arrangement in which the RhZn4 units are held together by Rh–Zn and Zn–Zn bonding Interest in the reactivity of the Zn– Zn bonded precursor [Cp*ZnZnCp*] (40) has continued in 2010 The new compounds 4191 and 4292 are obtained by controlled reactions of organic acids with 40 (which acts as a base and retains the Zn–Zn bond) and are the first examples of heteroleptic compounds of ZnI As in previous years, Hg organometallics formed an extremely extensive class of structurally-characterised compounds in 2010.93–110 Most of these were of the classic types [R2Hg] and [RHgX] (X=halide or a Organomet Chem., 2012, 38, 112–127 | 121 heteroatom-centred organic anion) Very few examples of p-bonding were observed in this area.110 A particularly interesting example is the observation of a Hg-Sb donor interaction in 43, which at 3.073(1) A˚ lies between the sum of the metallic and van der Waal’s radii of Hg and Sb (Fig 9).93 DFT calculations show that the occurrence of this interaction in 43 is the result of a unique iodide push–stibonium pull effect, which polarizes the diffuse closed shell of the mercury atom and thus promoting its engagement in a polar bonding interaction This is the first example of Hg behaving as a Lewis base A further occurrence of Hg metal bonding is seen in the behaviour of the metallophilic Mercuraazametalla-macrocycle 44 (Fig 10a) which has been shown to coordinate group 11 (M=Cu ỵ , Ag ỵ ) ions using Cp* Rh Cp* Me Zn *Cp Cl Zn Zn Zn Zn Zn Cl Me3Si Zn Zn Me Ph *Cp Rh Zn Zn Cp* Zn N N P P Ph Cp* 38 SiMe3 Zn Ar O Ph Ph N N N Ar N 41 42 (Ar = 2,6-Me2C6H3) Fig Structures of 38, 41 and 42 Fig (a) Structure of 43 (b) R N N Hg + Hg Hg N N N M N R N N 44 R = CH2CH2 Hg 46 R = 45 Fig 10 Structure of the Hg macrocyles 45 and 46, and b) the Cu ỵ and Ag ỵ complexes of 44 122 | Organomet Chem., 2012, 38, 112–127 (a) (b) Dipp Dipp Dipp N N Hg N N Dipp Dipp Dipp N Hg N Dipp N N Dipp 48 47 R = nPr, nBu Fig 11 a) Structure of 47 and b) solution equlibrium between the two linkage isomers of 48 a combination of donor the N-atoms and strong Hg metal Hg interactions (the cation complexes 45, Fig 10b).94 In the case of the macrocyle 46 (Fig 10a), however, cleavage of the cyclic framework occurs with Pd2 ỵ and Pt2 ỵ giving an arrangement which also contain 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