Ch. Elschenbroich, A. Salzer - Organometallics A Concise Introduction d EditionChristoph Elschenbroich { Albrecht Salzer Organometallics A Concise Introduction Second, Revised Edition CY | VCH" weinheim - New York - Basel » Cambridgeometalichemie, 3. Aufl German eitiON: prcich/ Salzer: Onganometall age aitgart, 1991: Elechen! BiG, Teubner, U0 henbroich prof De. Christoph Ebh Frente Chemie Phipps Unvversil Hane Mecrwei St Dotss0 Marburg Albrecht Salzer citut Marburg riv-Doz. Dt Pr tan cherisches Ins Daneriit Zach warren ae es gun apie do wr ilo cath el Nong ar ra yn oe at eh sa Tan era fr ct ro data illustrations, pro be Re Seti 2nd edition 1992 ised jin by 7 ran ia aft mbEL, Weinheim (Federal Republic of Germany) YH Pushes Ine, New York, NY (USA) Editorial Director: Karin von der Production Manager: Dipl.-Wirt-Ing. (FH) Bernd Riedel Cover design: TWI, H. Weisbrod, D-6943 Birkenau Library of Congress Card No. applied for A catalogue record for this book is available from the British Library Die Deutsche Bibliothek ~CIP-Einheitsaufnahme Elschenbroich, Christoph: Orgunometalis : « concise introduction / Christoph Elschenbroich ; Albrecht Salzer, ~2., rev. ed. - Weinheim ; New York; Batel; Cambridge: VCH, 1992 inheitssacht.: Organometalichemi¢ ¢e ISBN 3:527.28165-7 (Weinheim) __!SBN 0-89573-984-4 (New York) Ne: Salzer, Albrecht © VCH Verags Sserselichaft mbH, D-6940 Weinheim (Federal Republic of Germany), 1992 Printed on acid-free and low-chlorine Paper. ved (including th ‘eproduced intent 8 those of translation into other lat is book may ts i acne CMR motor any oe eae No eal ‘te. wsed in this book, Seen aout Writien permission from the publica Re te even when not specificall a ere norte tresescarela “Pecfically marked as such, are not to be considered unprotected B} tion: Graphischer riphicher Bae Re 2a rnc ee Wire ae conn 87 Phiecber Betrieb Konrad Tritsch, Dover? WosburgPreface to the Second Edition re ef 1 f pt to b a literature citations of work referred to in the text index the © Once again, we thank our publisher for splendid cooperation, in particular Karin von der Saal, w her gentle but persistent way helped to c the job in ti me for the Apart from ourselves, no one read the manuscript; so nobody else is to bl remaining errors and omissions. Ch. Elschenbroich A. Salzer Marburg 1991 Ziirich Germany SwitzerlandPreface t0 the First Edition 1 volume is the translation of the pani Béisos rae of our The present volume 'e Finfiihrung”; corrections and a few results hee Sopa eel the body was left unchanged. Bie. ig aoe. a branch of chemistry still be called “concise”? On the other 00 page treatise on a branch of chen FT Seen 1 ri of only 20 pages covering transition-metal oe plexes seit oe chort, This contrast illustrates the dilemma encountered if one sty oo a ole of organometallic chemistry in a single volume of tolerable size ay ine from an introductory course (one semester, about 30 lectutes) on o Seite i students confronted with the field for the first time de eee isa mixture of indispensible basic facts and selected results of most sreent vintage. Attempts to systematize organometallic chemistry by relating moleoular rmuctures to the number and nature of the valence electrons are presented as are applic ations of organometallics in organic synthesis and in industrial processes based on homogeneous catalysis. ‘Anapparent omission is the absence of a chapter specifically dealing with organometallic reaction mechanisms. It is our contention, however, that mechanistic organometallic chemistry has not yet reached the stage which would warrant a short overview from which useful generalizations could be drawn by the beginner. Note, for example, that even reactions as fundamental as metal carbonyl substitution are currently under active investigation, the intermediacy of 17 or 19 valence electron species opening up new possible pathways. Interspersed within the text, however, the reader finds several com> ments and mechanistic proposals ranging from well established kinetic studies to cata ysis loops which at times have more the character of mnemotechnic devices than of kinetic schemes based on experimental evidence. Detailed mechanistic considerations should be deferred to the second act of the study of organometallic chemistry and several textbooks, mainly concentrating on organotransition metal compounds, offer # wealth of materi with which to pursue this goal. eat poe the text in the traditional way ~ following the periodic table for tiandition-rpetal ee ean and according to the nature of the ligand for from the Chapters 7 nat ao al we find most suitable for an introduction. Apart specialized material 4 ae letal-metal bonds, clusters, catalysis) somewhat mOne Tfeencng would be inser noms called “Excursions”, Rigorous & survey 300 od ents ree bsiate ita text of the present scope. At the end, a ss key papers, including seston ice leads the reader to important review articles sf authors names are linked een in the field, Furthermore, in the running (ext hates the year of the discover we facts described whereby the form (Author, year) Year R) the appearance of analy ita short communication, and the form ( Fespective full paper or review. The complete out to portr:face VIN be easily retrieved via consultation of Ch the mical Abstracts. A desired side-effect is {o familiarize the student with author's names and their fields of endeavor. The many coworkers, who actually did the work, may forgive us that only the n tive boss is given Among our own coworkers who helped to bring this English Edition to completion, the native speakers Pamela Alean (Great Britain, now a resident of Zirich, Switzerland) and James Hurley (USA; resident of Marburg, Germany) stand out. They went a long way to eliminate our worst excesses of “Gerglish”. The bulk of the structural formulae was drawn by one of the authors (A.S.) thereby keeping things in the right perspective and. making the book easy to use. Monika Scheld, Marburg, helped with the preparation of the indexes and by checking the cross refer We are grateful to the editor Dr. Michael Weller and the production manager Bernd Riedel (both of VCH Publishers) for a pleasant form of cooperation and their toleration of several last-minute changes. Finally, the authors mutually acknowledge their unflagging support during the various stages of the enterprise. ame of the respec: Ch. Elschenbroich March A. Salzer Marburg 1989 Zarich Germany SwitzerlandContents Preface Introduction 1 Historical Development and Current Trends in Or ometalle Cheats 2 Demarcation and Classification of Organometallic Compounds 3 Energy, Polarity and Reactivity of the M~C Bond Lability of Main-Grouy MAIN-GROUP ORGANOMETALLICS 4 Methods of Preparation in Perspective 5 Alkali Organometallics Excursion: *Li and "L-NMR of Organoithim Compounds Organyls of the Heavier Alkali Metals Excursion: ESR Spectroscopy of Organoalkali Metal Compounds 6 Organometallics of Groups 2 and 12 6.1 Organometallics of the Alkaline Earths (Group 2) Organoberyllium Compounds Organomagnesium Compoun Organocalcium, -strontium and -barium Compounds Organometallics of Zn, Cd, Hg (Group 12) Organozinc Compounds Organocadmium Compounds Organomercury Compounds xeursion: Organomercury Compounds in vivo 7 Organometallics of the Boron Group (Group 13) 7.4 Organoboron Compounds 2 7A.1 Organoboranes . . . 38 40 o 48 4B 50 50 34 37 7 37— Carbaborancs and Heterocarb: Wipe NMR of Organoboron Compounds ee ‘Compounds ‘and Thallium Organyls “Gala of Ga a, Tl and thet Lew Base Complexes of Ga, In, and T! ft Ronons of Thallium ‘Organyls in Organic Sy Compounds ofthe Casbon Group (Grovp 14) ‘of Coordination Number 4 Organyls of Coordination Numbers Products | Organogermanium Compounds - ee Number 4 = ‘of Coordination Numbers 2eS, | Contents x Pt —_—_Senenis__ 3 66 ve 7s 86 12 The 18-Valence-Electron (18-VE) Rule ae 186 86 Excursion: Can the VSEPR concept (valence shell electronspair repulsion, © Gillespie-Nyholm model) be applied to transition-metal complexes? . 191 13 o-Donor Ligands °§ +» 193 4 13.1 Prey tion of Transition-Metal Alkyls and Aryis » 194 : i 13.2 Selected Properties of Transition-Metal o-Organometallics eee tet 13.21 Thermodynamic Stability versus Kinetic Lability 197 > 13.2.2 Transition-Metal o-Complexes in vivo 201 13.2.3 Transition-Mctal Perfluorocarbon a-Complexes » 204 ! 14 o-Donor/x-Acceptor Ligands - 206 Transition-Metal Alkenyls + 206 Transition-Metal Alkynyls Se 208 j ‘Transition-Metal Carbene Complexes... .. . . . 210 1 ‘Transition-Metal Carbyne Complexes 8 4 Metal Carbonyls Og ca ee 220 Preparation, Structure and Properties... . . . , ats seed Variants of CO Bridging... .,.,.,... eee Sage ; 5.3 Bonding in Metal Carbonyls, Theory and Experimental Evidence 226 14.5.4 Principal Reaction Types of Metal Carbonyls .. ..... .. . 232 r 14.5.5 Carbonylmetallates and Carbonyl Metal Hydrides... . . . . , 234 ie 14.5.6 Carbonyl Metal Halides . . . . . athe une paren =, Aen: 14.6 Thio-, Seleno-, and Tellurocarbonyl Metal Complexes. . . . . . . 4 is 14.7 _Isocyanide Complexes (Metal Isonitriles) . . . sw ww ia _ Excursion: Photochemical Reactivity of Organotransition Metal Complexes . 242 Lanai choca int ha eet te sysiaiieay ephewibhtite 2 Sa eomenhamegzs « 1 Homoalkene Complexes)... 2 oeNomenclature of Organometallic Compounds Author IndexIntroduction 1 Historical Development and Current Trends j aan rends in Organometallic 1760 ‘The cradle of organometallic chemistry is a Paris militar cy. Iti sa Paris y pharmacy. Itis there that Cadet works on sympathetic inks based on cobalt salts, For the uses cobalt minerals which contain arsenic. ss anna As;0y + 4.CH,;COOK ——+"Cadet’s fuming liquid” contains cacodyloxide {(CH,);As],0 (waxeoing = malodorous) first organometallic compound 1827 Zeise’s salt Na{PtCl,C,H,], first olefin complex 1840 R.W. Bunsen continues the study of cacodyl compounds which he names “alkarsines”, The weakness of the As—As bond in molecules of the type R,As—ASR, led to a profusion of derivatives like (CH)sAsCN whose taste (I)is checked by Bunsen. 1849 E, Frankland, student of Bunsen’s at Marburg, attempts the preparation of an “ethyl radical” (cacodyl as well was taken to be a radical). (++ Znl, + 2C,Hs |__, (C,H,),Zn (a pyrophoric liquid) $ + C,HZnl (a solid) + Znls J 3C,HgI + 3Zn—SiCl, + m/2 ZR, —* RpSiClam + 71/2 ZnCl, 4J,A.Wanklyn develops a method for the synthesis of halide-free mag ~(GiHs),He + Me—* (C,H,).Me + He predicted: found: Eka-Si(CjHs)4 Ge(C,Hs), (C. Winkler, 1887) d= 0.96 d=0.99 bp: 160°C bp: 163.5°C (CO),, first binary metal carbonyl, used in a commercial process for Mond is the founder of the English company ICI (Imperial Chem. ‘as well as a renowned collector and patron of the arts. ‘Mg for Zn in reactions with alkyl iodides: ne On )e-CH-CH,-C-CH, H,C CH, student V. Grignard (Nobel prize 1912 shared itive than ZnR, RMgxX is a more potent alkyl1919 1922 1928 1929 1930 1931 1938 1939 1943 jelopment and Current Treads in Organometallic. Chemistry F. Hein from CrCl, and PhMgBr synthesizes polyphen now known to be sandwich complexes, Pelyphenyichrconus-comgotaie T. Midgley and T. A. Boyd introduce Pb(CH,), as ck addi So 2H), as an antiknock additive in W. Hieber inaugurates his systematic study of metal carbonyls Fe(CO), + H,NCH,CH » (H,NCH,CH,NH,)Fe(CO) 200 Fe(CO), +X; —> Fe a aoe 2+ CO F. A. Paneth generates alkyl radicals through PbR, pyrolysis, radical identifica- tion by means of their ability to cause the transport of a metallic mirror. Paneth thus reaches a goal set by Frankland in 1849. K. Ziegler encourages more extensive use of organolithium compounds in synthe- sis by developing a simpler way of preparation, PhCH,OMe + 2Li—— PhCH,Li + MeOLi (ether cleavage) H, Gilman: RX + 2Li——+ RLi + LiX (procedure used today) W. Hieber prepares Fe(CO),H,, first transition-metal hydride complex. 0. Roelen discovers hydroformylation (the oxo process). \W. Reppe starts work on the transition-metal catalyzed reactions of acetylenes. E. G. Rochow: 2CH,Cl + Si SS, (CH,),SiCI, +... ; = ‘This “direct synthesis” triggers large scale production and use of silicones. Prelim inary work by R. Milller (Radebeul near Dresden) was interrupted by the Second World War. : P. Pauson (GB) and S. A. Miller (USA) obtain ferrocene (CsHs);Fe, first sand ‘wich complex. aon ect Sein: Pratersion of eyelobutadiene by complexation in (Cy by H. C. Longuet-Higgins and L.. Or 1495) Cy (PPhy)al(COVC! reversibly binds O2. ive to K. Ziegler and G. Natta. (CO)sWC(OMe)Me, first carbene complex.rical Development and Curres or t Trends in Organometallic Chemistry 5 (Current Trends ah @ Participation of higher main-group elements in p,~p, multiple bonds Examples! O Z si ‘ " cessible in the gasphase Arsaalkyne Distibe tine, accessible in the gasp! y istibene Sorin marx isolation Rory Raa: e @ Stabilization of highly reactive species by metal coordination Examples: cyclobuta c, carbyne, thiocarbonyl, selenoformaldehyde. Ook. te Fe (Me3CO)gW = : a Sle Barca co @ Metallacycles Examples: (AgCl) (CR)Os(CO) (PR3),C1 Cp,W—CH,—CH,—CHmetallic Chemistry s in the hydroformy) her-Tropsch chemistr iON reac , alkene 700.000 t/a 600.000 t/a (declining)= 2 Demarcation and Classification of Organometallic Compounds ometallic compounds (metal organyls, organometall terials Eee goes direct, more or less polar bonds M!* — ce ee atoms. In many respects, the organic chemistry of the elements B, Si, P and As resembles the chemistry of the respective metallic homologues. Therefore, the term organoelement ‘compounds is used occasionally in order to include for consideration the aforementioned non-and semi-metals. A convenient classification of organometallicsis based on the bond type: 1 fa] J ILi ft Be} v Cr Mn Fe Co 8c. Ti Y Zr Nb Mo Te Ru Rh La* HE Ta W Re Os Ir Ptrs debond is defined as follows Number of nodal Planes including the Bond Axis the clectronegativity difference betwe Is ay 1c ween the neigh Me eectroncgativity values in table 2-1 cee hod of determination: es‘he element hydrides, however, the dependence ofthe ele ee the hytridtcation ratio has to be taken co asenter aan BO ss are expored to a stronger effective nadie charge than p electrons of the an ipal quantum number, EN (C) increases with increasing ctronegativity of earbon ‘ganoelement compounds, 8 character in the hybrid: EN(Gyp) = 25 applies to sp” hybridized carbon, whereas for cases of Migher Be the values EN(Cyp) = 275 and EN(C,) = 329 have been proposed MEME ey. This gradation alto refects the increate Ge CH acidity according to -. _ C,H, < C,Hs and suggests that the M—C bond is considerably more polar in Bee cal complexes (p. 208) than in metal alk) aikynyimetal com! . Furthermore, it should not be over- ed that in compounds of the type L,M_~CRs, the electronegativity ofthe metal EN(M) nd by the ligands Land the electronegativity of carbon EN(C) by the groupe ee Bein ifreke eondept of electronegativity and its applications is found in R "E Huheey, Inorganic Chemistry ~ Principles of Structure and Reactivity, New York: ee ‘and Row, 1983. lization, it may be stated that the chemistry of main-group organometal- ee. ty the group the metal belongs to, whereas for organotransition-metal Be ates the nature of the ligand dominates Consngoenty the metal in I 14:3 arranged in conformity with the periodic table, while that ofchinplem 49 je presented according to the types of ligand. angele.Jofthe properties of organometallics itis important to distin, c unstable) and kinetic (inert, labile) factors fare encountered throughout the periodic table (exam, flaMeg), WMe,). For organotransition-metal c oa Me, Pare derived from the large number of valence orbitals and yeu ‘atoms to engage in multiple bonding (sec ite Buish between © bond lengths d in pm and calculated covalent radii r for main-groy 4-71. £rOUp clemens3. Stability of Main. 31 Stability of Main-grou — CoP Oresnometalics it 4: Comparison of standard enthalpies AH in mol and mean Table > bond enthalpies Fees of etl derivatives inthe gas phase with values EQM XY oe FO-Cn ea See a MMe, MMe, oe > aaa: MMos 3 ant uke MA eg MME Bo W123 365 <1607 358° eet ae aes Al <5 St -MS ML PL 6 ME AW) Ga 42 267 ~ MWA 3 cages eee en ie io ne Ss se 2m on 136 152 Bi ak aah B-o 326 -o 452. MO" 3 oF B-Cl 456 cl 31 Bi-al mm Al-O $00 =F 6s Al-cl 20 ‘se-a 23 ‘Dota for M—C: Comprehensive Organometallic Chemistry, 1 (1982)5 ‘Dota for M—X: J. E. Huheey, Inorganic Chemistry, 3. Ed., A-32‘and Reactivity of the M—C Bond cover # wide range (CHy)sB (CH,),As Chi nol 365 relatively strong medium egy E(M —O)within a main-group decreases with increag dalso applies to the bonds of M to other elements of the a8 "Ome “this effect is the increasing disparity in the radial exten 24 to ble overlap of the atomic orbitals contributing to the yp 84 6on s encountered if M is particularly electropositive and/or thy 9.6, Pd Carbanion lension ‘i NICHI. K*(CPh]”, Na*([C=Cr} deficient bond”) arises if the valence shel, OM ay td the cation M** is strongly polarizing (possesses a large dng ‘a . i) Vvior of organometallics which are based on the respective meet with limited success because usuall : , ly, rather than ‘other, more complicated decomposition pathways arettomie d row, 1 con. anion ive «for PYCH,), than Fue cron 0 -nination to occu ite aay that the f-climination mect T umPortant role for the organometalicg cof groups 1, 2 and 13 (valence configurations s!, 5? and s? ) than for those of groups 14, t5and 16(5°p*, s*p? and s* p. Ifa binary o eanometallic species has an empty coordi, nation site at its disposal, f-climination can be blocked ang thermal stability increased through formation of a Lewis base adduct (Example (bipy)Be(C,H,),, bipy - 2 bipyridy!). B-Elimination assumes a position of i the chemis ‘organotransition-metal compounds (chapter 13), ray As with organic compounds, all organometallic materials are thermodynamically un- stable with tespect to oxidation to MO,, HO and CO, New 4 theless, large differences in the ease of handling of organometallic are encountered which may be traced back to differences in kinetic intertness, Example: Heat of Thermo- Property Kinetics combustion dynamics Zo(CH.)s 1920i/mol_ unstable) gypaphods So(CH,). —3590 ki/mol unstable airstable inert Particularly labile against ©, and HO are organometallic molecules which possess free electron pairs, low lying empty orbitals and/or high polarity of the M—C bonds. Com- In air: In water: Relevant factors: pyrophoric hydrolysed electron gap at In, high bond polarity. inert inert Pyrophoric inMAIN-GROUP ORGANOMETALLICS 4 Methods of Preparation in Perspective ures for the formation of bonds between main-group me roughly be divided into the following reaction types: ? télé and carbon may oxidative addition [1], exchange [2]~[7], insertion [¥)- 10] and climination - fp). Direct Synthesis [7] 2M +nRX—~+ RM + MX, (or RMX) Examples : 2Li+ C,HyBr Mg + CcH3Br —>+ CyHoLi + LiBr + CoH sMgBr ‘The high enthalpy of formation of the salt MX, generally renders this reaction exother- mic. This is, however, not true for elements of high atomic number (M = TI, Pb, Bi, Hg) which form weak M—C bonds. Here AH?(R,M)>0 is not compensated for by ‘AH}(MX,) <0 and an additional contribution to the driving force must be provided. ‘One possibility is the use of an alloy which, in addition to the metal to be alkylated, contains a strongly clectropositive element. Mixed Metal Synthesis 2Na + Hg + 2CH,Br— (CH),Hg +2NaBr AH =~ $30ki/mol 4NaPb + 4CHsCl —> (C,H,),Pb + 3Pb + 4NaCl 3 {AH} (NaX) boosts the driving force] ir very nature direct syntheses are oxidative additions of RX to M° whereby RM"X The generation of new M—C bonds by means of the addition of RX to aExchay_ RM + R'M’—— R'M + RM “change 4PoLi + (CH. =CH),Sn — 4(CH, =CH)Li + PhS on of Ph,Sn shifts this equilibrium to the right and good yield, F Vinglthium is accessible by other methods only with g ue Mi culty. am + Metal Halide Metatheaig RM + MX ——> RM’ + MX Q 3.CH,Li + SbCl, —> (CH,),Sb + 3 Lici m lies on the side of the products if M is mor: ‘metal organyl, this procedure has wide applicability si large contribution to the driving force. H RM + RX ——> RX + R'M n-BuLi + PhX ——> n-BuX + PhLi mn is practicable for ary! halides only Br gare are alkylation (Wurtz coupling) and the metalation of R cae ywever, a comparatively fast reaction and is favored at low tema \per- rs : ideas include the intermediate formation of idea nediate f radicals , metal halogen exchange is initiated by a single peor of ne Ee ‘Mereuric Salt + C—H Acid By their very nature, mercurations are also metallations, In the case of moearomatic bstrates, they are confined 10 molecules of high CH-acidity alkynes, carbonyl, mites, halogeno-, cyano compounds etc). » nitro-, Hg[N(SiMes),], + 2CH,COCH, * (CH,COCH,),Hg + 2HN(SiMe,), IfHg(CH,COO), is used as a mercurating agent, the second step usually requires forcing conditions. A reaction of very wide scope is the mereuration of aromatic compounds: Hg(CH,COO), + ArH —M20# ArHg(CH,COO) + CH,COOH From a mechanistic point of view, this reaction is an electrophilic aromatic substitution. ‘Metal Hydride + Alkene (Alkyne) Hydrometallation ee fed MOH + (CnC, ———-3 UG Acuah 7 M=B, Al; Si, Ge, Sn, Pb; Zr (C,H;),AIH_ + C,H, ——>(C,Hs);Al_ Hydroalumination SiH < Ge-H Lix + H,0 is inapplicable since alkoxides, stemming from the reaction of RLi with O, or from ether cleavage, would suggest too high an RLi content. Therefore, a double titration method has been developed (Gilman, 1964). The RLi concentration amounts to the difference i+nmROLi+(m+n)HX = ——+mRH+nROH +(m+n)LiX on Pet nr RCIY chock wecked dard (~ 4.9 pet oRCy Lu) of org olithium compounds is their tendency to : i ‘the solid state, A classic example is the sty " bribed ias cubic body. askin, atc 2 Bra with methyl groups capping the te? (b) Schematic drawing of the un A(Li=C) @ Bi pm (CH, ALis-C)= 26pm (Lich, 268 pm (LICH, 267 pm Li ig) 304 pm d “ae With alternate occupation of the rrangement is encounterod Is that the methyl groups of one (LICH), tetrahedron. These intermolecular ubility of LiCH, in non-solvating hyllithium, the intermoleculat s strongly dependent ooe $1 Organolithium Compounds 2 ‘Agstezation THE, Ft,0. : tetramer (Li, tetrahedro Me,NCH,CH,NMe.(TMEDA) eee cyclohexane hexamer” E10 THE dimer tetramer hydrocarbon tetramer monomer : THR, E1,0 pts THF, E1,0 monomer rie E,0 solummar structure (p23) - x ts, eS ence of oligomers (LiR), in solution is substantiated by osmometric measure- Li:NMR spectroscopy and by ESR experiments (p. 35), ‘The mass-spectromet- 4 ic ervation of the fragment ion {Li,(t-Bu),]* shows that the association is maintained Lg 4 NMR studies by T. L. Brown (1970, R) and by G. Fraenkel (1984, R) have that, much like Grignard reagents (p. 43), solutions of organolithium compounds complicated equilibrium mixtures. The dynamic processes in these solutions com. ‘intramolecular bond fluctuatic In the case of \(-Bu)Lil, at = 22°C 8C{H}NMR features. a septet caused by coupling to the = SE ete three nearest neighbour °Li muclei, ‘JCC, *Li) = 5.4 Hz, coupling to the remote °Li nuclei not being re- % solved. At — $°C in the fast flux- ional limit a nonet is observed, @= "cx J¢PC, *Li) = 41 He, which repre- * sents the weighted average of the three adjacent and the vanishingly small remote couplings (Thomas,ganometal 5 Alkali On Seni 2 pacenters of te OCS are strongly influenced by the mate of ye The kinetic A ind the group * 7 ete ranolithium compounds 10 associate iD the solid state as welt he wendeney of ortaot that in a single molecule LiR, the number of valence een uc 10 solution is ft a Li valence orbitals for two-electron twonene 3 js 100 low to vse all oe TLiR), this “electron deficiency” is compensated fog tae i ponding, In the 4BereBAl6s 1. "Taig js illustrated for the tetrahedral species ( the lticenter LiCH formation of m Li Lis skeleton with 4Li(sp”) hybrid orbitals per Li atom. Directional prop- is shelton wi ; ti lence orbitals: ei i hoe of te hreol oxs of raed a i rr of the triangular faces 3 tangentiat, pointing cowards the m0 rmals of the triang! i i Li ic © cst eal eae Sconce rapa " ui originating at the cores L8e a, LENO Trios ote b c 3 Four-center bonding molecular orbital from the interaction of Li, group orbital a with a C(sp*) hybrid orbital. This 4c-MO is Li—C as well as Li-Li bonding. The clectronegativity difference between lithium and carbon should manifest i 2e4c bonding pair of electrons being located closer to the carbon than to ‘the: ee Ps bond polarity Li?* —C*~ can be demonstrated experimentally, eg. by. dipole soon LiCH, molecules in matrix isolation were reported to po ép aie s Bebe 6 Debye (Andrews, 1967), a value of 9.5 Debye being ee charge separation (ionic limit), The degree of covalent ape é ~C bond is still an open question; sizeable covalent contribu Ty ones authors (Lipscomb, 1980; Abirichs, 1986) and essentially | character (Streitwieser, 1976; v, Ragué Schleyer, 1988R). iz