4S Ch. Elschenbroich, A. Salzer Organometallics ~' A Concise Introduction |. Revised EditionChristoph Elschenbroich Albrecht Salzer Organometallics A Concise Introduction Second. Revised Edition >) VCH Weinheim - New York - Basel » Cambridge.the German cat gehenbroicl Salzer Organometalichemie, 3. Aufl, Srutigart, 1991: FI sjschenbroich rublisher of BG Teubnet. prof Dr Chnistoplt E Fachbereich Chem | ailpps Universitat Marbure Hans Meerwein-Str [p-3550 Marburg voz. Dr. Albrecht Salzer Fan cheisches Institut Universitit Zarich Winterthurer Str. 190 CH-8057 Zarich Jess, authors and publisher do not warrant the informa: carefully produced. Neverthe! This book wan carefully PeDOiE of errors. Readers are advised to Keep in mind that sta tom contained er cedura details oF other tems may inadvertently be inaccurate ements, data, , 2nd edition 1992 Published jointly by : VCH Verlagsgeselischaft mbH, Weinheim (Federal Republic of Germany) VCH Publishers Inc., New York, NY (USA) Editorial Director: Karin von der Saal 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 Eschebroch, Christoph: reanometallics : a concise introduction / Christoph Ekchenbroich Albrecht Salzer. ~ 2, rev. ed. Weinheim : fen York: Bae Cambridge : VCH, 1992 . cht.: Organometallche ISBN 3.527.28165-7 (Weinheim ..) a ISBN 0-89573-984-4 (New York) | Ne: Salzer, Albrecht: © VCH Verlagsgeselt ee feseltchafl mbH, D-6940 Weinheim (Federal Republic of Germany), 1992 on acid-free and low-chlorine paper All rights reserved (i part of this book eserved (includ ' inary ing those of translation into other ges) si sored Cig to aa ito : chine 7 ty ther erating, microfilm, or any other meng 7 nor ibd ort a machi 5 ane ‘when not {ct Permission from the publishers. Registered names, t book, even when Specifically marked as such, are not to be considered ion: Graphischer Betti : Graphischer Renin nie Konrad ‘Til 7 bindin Graphite ge Konrad Tauck, DOORN Konrad Thitseh, D-8700 WirsburgPreface to the Second Edition To revise, according to the Oxford American Dictionary, means to reexamine-and alter or correct. That is what we have done in this Second Edition which is characterized by elimination of errors, substitution of old examples with new ones, which illustrate certain statements more effectively, and addition of recent findings which are apt to become landmarks. From the last category, the following entries should be mentioned: the fundamental new main-group clement clusters R4B,, R,Al2; , and Cpt Alj, the hete- rocycle tellurepin; the first stable carbonyl complex of silver, Ag(CO) [B(OTeF.),}; the coordination of buckminsterfullerene to platinum; the unsupported Co=Co double bond in Cp*Co=CoCp*; and the stabilization of the disilylene Me,Si, through coordi- nation to tungsten (the cover molecule). Further important additions include mention of homogeneous Ziegler-Natta type catalysts based on Cp,ZrMe* derivatives, the pre- scription of how to arrive at the “magic numbers” which are supposed to govern cluster geometries, an extension of the section on CH activation, and a very brief treatment of organolanthanoid chemistry, which concludes the final chapter of the book. Allin all, we have made more than a hundred small changes, overt and covert, which may escape immediate detection since we have kept the format of the book virtually un- changed (A Concise Introduction). However, in order to lure the reader into looking up further details of interesting results, we now give in the author index. the complete literature citations of work referred to in the text. Once again, we thank our publisher for splendid cooperation, in particular Karin -von der Saal, who in her gentle but persistent way helped to complete the job in time: Apart from ourselves, no one read the manuscript; so nobody else is to blame for the remaining errors and omissions. Ch. Elschenbroich: November ‘A Salzer Marburg 1991 GermanyPreface to the First Edition The present volume Is the translation of the cassie eaten haw Of Our: text present YON gine kurze Einfihrung”. corrections and a few results of yepy -Organometallchemic | ® the body was left unchanged. Y vay were included but otherwise the rchanged. recent a ve treatise ona branch of chemistry still be called “concise”? On the other: Can a 500 page ff only 20 pages covering transition-metal olefin complexes certaj sain Petal short This contrast illustrates the dilemma encountered if one sets nahin ‘neal the whole of organometallic chemistry 1n a single volume of tolerablesige. The book developed from an introductory course (one semester. about 30 lectures) on organometallic chemistry for students confronted with the field for the first time. The material covered is a mixture of indispensible basic facts and selected results of most recent vintage. Attempts to systematize organometallic chemistry by relating molecular structures to the number and nature of the valence electrons are presented as are appli- cations of organometallics in organic synthesis and in industrial processes basedon homogeneous catalysis. An apparent 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 catal- ysis loops which at times have more the character of mnemotechnic devices than of kinetic schemes based on experimental evidence. Detailed mechanistic considerations ara paaiiiel to the second act of the study of organometallic chemistry and several of material with ‘Which te carey organotransition metal compounds, offer a wealth We have structured the text in the ‘raditional way ~ following the periodic table for main-group element organometallics and Oe temo ligand for transition-metal complenes whic an according to the nature of the | : from the Chapters 16 and ya ie ne find most suitable for an introduction. specialized material is freee etal -metal bonds, clusters, catalysis) somewhat more Teferencing would be ina tii 7 sections called “Excursions”. Rigorous s¢ survey (300 odd entries) ie gi ‘ate in a text of the present scope. At the end, @ lite key papers, includin, is given which leads the reader to important review articles authors names are liked classics in the field. Furthermore, in the running hates the year of the disconge son's sesetibed whereby the form (Author, yea) year R) the appearance of te usually in a short communication, and the form ( Tespective full paper or review. The complete cit PPropiPreface vu then be easily retrieved via consultation of Chemical Abstracts. A desired side-effect is to 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 name of the respec- 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 u resident of Ziirich, 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 references. 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. Ch. Elschenbroich March A. Salzer Marburg 1989 Zirich Germany SwitzerlandContents Preface Introduction © 2. 0 ee 1 1 Historical Development and Current Trends in Organometallic Chemistry ... 1 2 Demarcation and Classification of Organometallic Compounds. . . . . . . - 7 3 Energy, Polarity and Reactivity of the M-C Bond .....- 1... ~~~ 10 3.4 Stability of Main-Group Organometallics . 2... 2... 5+: 10 3.2 Lability of Main-Group Organometallics... 2...) + 7 7 es 12 MAIN-GROUP ORGANOMETALLICS 4 Methods of Preparation in Perspective . ©. ©... ee ee et 15 5 Alkali Organometallics 2 2 2 2 1. 19 SA Organolithium Compounds...) ee 19 Excursion: °Li- and 7Li-NMR of Organolithium Compounds ...... - 24 5.2 Organyls of the Heavier Alkali Metals. 2 6 6 6 ee 2 ees 33 Excursion: ESR Spectroscopy of Organoalkali Metal Compounds. . . . . - 35 6 Organometallics of Groups 2 and 12... 2 2 6 1 2 es 38 61 Organometallics of the Alkaline Earths (Group 2)... - . + + + > 38 6.1.1 Organoberyllium Compounds... . - - ee ee et 38 6.1.2 Organomagnesium Compounds... 2. 40 6.1.3 Organocalcium, -strontium and -barium Compounds .....- - - 47 6.2 Organometallics of Zn, Cd, Hg (Group 12)... - 2. ee 4B 6.2.1 Organozinc Compounds... 6) - ee ee 48 6.2.2. Organocadmium Compounds 50 6.2.3. Organomercury Compounds . . 50 Excursion: Organomercury Compounds in vivo. . . . . / + +s .. 54 7 Organometallics of the Boron Group (Group 13). © 2 2 2 6 2 et 57 TA Organoboron Compounds... - et 57 74.1 Organoboranes. 2 2 2. 57x Contents 71.2 Boron Heterocycles 2 0 0) 2 ee 7A3 Polyhedral Boranes, Carbaboranes and Heterocarbaboranes Excursion: ''B-NMR of Organoboron Compounds... . .--. - + = 72 Organoaluminum Compounds .... 2... 2-5-0: 13 Gallium-, Indium-, and Thallium Organyls . 2... 7.3.1 o Organyls of Ga, In, Tl and their Lewis-Base Adducts . . . . 73.2 «Complexes of Ga,In,andTl . 2... ee ee 7.3.3. Applications of Thallium Organyls in Organic Synthesis 8 Organoelement Compounds of the Carbon Group (Group 14)... . . . . 8.4 Organosilicon Compounds... . . 2-2-2 22 8.1.1 Silicon Organyls of Coordination Number 9 8.1.2. Silicon Organyls of Coordination Numbers 2 and 3 and their Subsequent Products 2... 2... ee ee 8.2 Organogermanium Compounds... ... 2... 0.2... 8.2.1 Germanium Organyls of Coordination Number4 ... 2... - 8.2.2. Germanium Organyls of Coordination Numbers 2 and 3 and their Subsequent Products ©... 2... ee 8.3 Organotin Compounds . 2... 2... ee Excursion: ''°Sn-Méssbauer and '!°Sn-NMR Spectroscopy... . . . . 8.3.1 Sn Organyls of Coordination Numbers 4,5,and6... 2... 8.3.2. Sn Organyls of Coordination Numbers 2and3 ........~. 8.4 Organolead Compounds... ................ 841 Pb Organyls 2. 84.2 Pb™- and Pb" Organyls 2... ee . 9.4.1 10 Organoelement Compounds of Selenium and Tellurium (Group 16)... . . 11 Organometallics of Copper, Silver and Gold (Group 11)... 2. 2... 11.1 Copper- and Silver Organyls 2... . 2.2 ee ee 14.2 GoldOrganys 2.2... ee ee Organoelement Compounds of the Nitrogen Group (Group 15)... 2... OA Element’ Organyls (E = As, Sb, Bil). 2 2 9.1.1 Pentaorganoelement CompoundsR,E..........00- 9.1.2 Organoelement Derivatives R,EX;_, . 2. 0-0 ee ee 9.2 Element Organyls (E = As, Sb, Bi). 2 2. 9.2.1 Trisorganoclement Compounds R3E.........0..02.. 9.2.2 Organoelement Derivatives R,EX;-, . . 00. ee ee 9.3 Chains and Rings containing E—E Single Bonds... 2... . 9.4 E=C and E=E Multiple Bonds 2. 2. ee C(p,—p,) Bonds 2... ee 94.2 E=E(p,-p) Bonds... ............ 000.Contents ORGANOMETALLIC COMPOUNDS OF THE TRANSITION ELEMENTS 12 The 18-Valence-Electron (I8-VE) Rule 2 2. 2 2 2 2 2 ee ee ee Excursion: Can the VSEPR concept (valence ‘shell electron-pair repulsion, Gillespie-Nyholm model) be applied to transition-metal complexes? . 13 o-Donor Ligands ©. ee 13.1 Preparation of Transition-Metal Alkyls and Aryls . . 2... . 13.2 Selected Properties of Transition-Metal o-Organometallics . . . . . 13.2.1 Thermodynamic Stability versus Kinetic Lability ©. 2... 2. 13.2.2 Transition-Metal o-Complexes in vivo ©. 2... 7. ee eee 13.2.3 Transition-Metal Perfluorocarbon o-Complexes ......-. 14 o-Donor/x-Acceptor Ligands © ©. 2... ee ee 14.1 Transition-Metal Alkenyls. . 2. 6. ee ee ee ee 14.2 Transition-Metal Alkynyls . 2... 2. ee ee ee eee 14.3 Transition-Metal Carbene Complexes. . . . « peepee 14.4 Transition-Metal Carbyne Complexes. 2 6 2 2 2 ee 14.5 Metal Carbonyls. © 2... 0 ee 14.5.1. Preparation, Structure and Properties. . ©... 21 eee 14.5.2. Variants of CO Bridging ©... 1. ee 14.5.3. Bonding in Metal Carbonyls, Theory and Experimental Evidence 14.5.4 Principal Reaction Types of Metal Carbonyls ......-.--- 14.5.5 Carbonylmetallates and Carbonyl Metal Hydrides... - - - ~~ 14.5.6 Carbonyl Metal Halides 2... 2. 1 ee ee ee ee 14.6 Thio-, Seleno-, and Tellurocarbonyl Metal Complexes. . . . . . - 14.7 Isocyanide Complexes (Metal Isonitriles) . 2... 25. - ee Excursion: Photochemical Reactivity of Organotransition Metal Complexes . 15 G, n-Donor/n-Acceptor Ligands 1 2. ee 15.1 Olefin Complexes 2. 0. 0 ee 15.1.1 Homoalkene Complexes... 2 7. 2 0 ee ee ee 15.1.2 Heteroalkene Complexes... 2 2. 1 ee ee ee 152 Alkyne Complexes. 0 0 ee 15.2.1. Homoalkyne Complexes 2... 6 6 0 ee 15.2.2 Heteroalkyne Complexes . 2... ee 15.3 Allyland Enyl Complexes... 2 0 02 ee 15.34 Allyl Complexes... 0.2. es 15.3.2. Dienyl and Trienyl Complexes. 2 2. 2 2 ee Excursion: 13C- and H-NMR Spectroscopy of Organometallics . . . . - - 15.4 Complexes of the Cyclic x-Perimeters C,H, . . . + 2 0 + se > 15.4.1 CsRfasaLigand. 2... ee 15.4.2 C,H,asaLigand 2... 15.43 CyHy asaLligand ee ee XIXi Contents 45.4.3.1 Binary Cyclopentadienyl Transition-Metal Complexes 15.4.3.2 Cyclopentadienyl Metal Carbonyls. 2... 0.0.00. ee 15.4.3.3 Cyclopentadienyl Metal Nitrosyls .............-- 15.4.3.4 Cyclopentadienyl Metal Hydrides 2... 2. 2. ee 15.4.3.5 Cyclopentadienyl Metal Halides . 2... 1... 154.4 CoH,asaLigand 2... 2... LL. 15.4.4.1 Bis(arene)metal Complexes... 2... ee 15.4.4.2 Arene Metal Carbonyls. 2 2 2 2 ee 15.4.4.3 Other Complexes of the General Type (n°-ArH)ML, 15.4.4.4 Benzene Cyclopentadieny! Metal Complexes. . . . . 15.4.5 CyH}asaLigand. .... 2... ee 15.4.6 CgHgasaLigand .. 2... ee ee Excursion: Transition Metal NMR in Organometallic Chemistry. . . . . . 370 15.5 Metal x-Complexes of Heterocycles 2... 2.2... 2... 376 15.5.1. Nitrogen-, Phosphorus- and Sulfur Heterocycles as Ligands . . . . 376 15.5.2 Boron Heterocycles as Ligands... 2... . 22.02.00. 380 15.5.3. Boron-Nitrogen Heterocycles ................0. 385 16 Metal—Metal Bonds and Transition Metal Atom Clusters .. 2... 2. . 386 16.1 Formation and Criteria of Metal—Metal Bonds . 2 2 2 2 2... 386 16.2 Dinuclear Clusters. 2 2. 1 ee ee 390 16.3 Trinuclear clusters © 2 2 1 ee ee ee 392 16.4 Tetranuclear Clusters. 2. 2 ee ee 395 Excursion: Structure and Bonding Conditions in Clusters, the Isolobal Analogy 20. ee 396 16.5 Approaches to Systematic Cluster Synthesis... 2... 1. 402 16.6 Pentanuclear and Higher Nuclearity Clusters 2 2... 0... 405 17 Organometallic Catalysis . . 2... . : o... 4tt 1A Catalytic Reactions and the 16/18 VE Rule ee se . 412 17.2 Transition Metal Assisted Valence Isomerizations. . . . . . » » 415 Excursion: Interaction of Transition Metal Fragments with Cyclopropanes . 416 17.3. Isomerization of Unsaturated Molecules .........2.2.. 418 17.4 Arylation/Vinylation of Olefins (Heck Reaction)... . 2... . 419 17.5 Alkene Metathesis ©. 2 2 ee en 419 17.6 Oligomerization and Polymerization .............4. 421 17.7 Olefin Oxidation (Wacker Process). 2 2. 2... 2. . » 425 17.8 Hydrogenation of Alkenes 2. 2 2 2. 2. ee 17.9 Fischer-Tropsch Reactions ...............00.4 17.10 | The Water-Gas Shift Reaction. 2. 2 2... 0. 17.11 Monsanto Acetic Acid Process... 2 2... 2.2... 17.12 Hydroformylation (Oxo Reaction) 17.13 Hydrocyanation.. .................-00.. 17.14 Reppe Carbonylation. ©... 0... 17.15 Activation of C—H Bonds in Alkanes - a Topical Problem in Organometallic Research... 2... 2. ee ee 439Contents XII] 18 Literature 446 Appendix 463 PRIM Symbols and Abbreviations |) To 463 Nomenclature of Organometallic Compounds eile! 465 Author Index. 2 468Introduction 1 Historical Development and Current Trends in Organometallic Chemistry 1760 1827 1849 1852 1852 The cradle of organometallic chemistry is a Paris military pharmacy. It is there that Cadet works on sympathetic inks based on cobalt salts. For their preparation, he uses cobalt minerals which contain arsenic. As,0, + 4CH,COOK ——>“Cadet’s fuming liquid” contains cacodyloxide ((CH,),As],0 (xaxeodng = malodorous) “first organometallic compound Zeise’s salt’Na[PtCl,C,H,], first olefin complex 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 (CH3),AsCN whose taste (!) is checked by Bunsen. 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,H, 3C,HsI + 3Zn — '—.. (C,H;),Zn (a pyrophoric liquid) ~ + C,H;Znl (a solid) + ZnI, Frankland possesses admirable skill in the manipulation of air-sensitive com- pounds. As a protective atmosphere he uses hydrogen gas! Frankland prepares the important alkylmercury compounds: 2CH,X + 2Na/Hg —— (CH,),Hg + 2NaX additionally: (C,H,),Sn, (CH,)3B (1860). In the following years, alkyl transfer reactions using R,Hg and R,Zn serve in the synthesis of numerous main-group organometallics. Frankland also introduced the concept of valency (‘‘combining power”) and the term organometallic. C. J. Léwig and M. E. Schweizer in Zirich first prepare (C,H;),Pb from ethyl- iodide and Na/Pb alloy. In a similar manner, they also obtain (C,H;),Sb and (C2Hs)3Bi.1859 1863 1866 1868 4871 1890 1899 1901 1909 1909 1917 1 Historical Development and Current Trends in Organometallic Chemistry W. Hallwachs and A. Schafarik generate alkylaluminum iodides: 2Al + 3RI—— R, All + RAII, C. Friedel and J. M. Crafts prepare organochlorosilanes: SiCL, + m/2 ZnR, —— R,,SiClam + m/2 ZnCl, J. A. Wanklyn develops a method for the synthesis of halide-free magnesium alkyls: (C,Hs)2He + Mg — (C2Hs)2Mg + Hg M. P. Schiitzenberger obtains [Pt(CO)CI,],, first metal carbonyl complex. D. I. Mendeleev uses organometallic compounds as test cases for his periodic table. Example: Known: predicted: found: Si(C,Hs), Eka-Si(C,Hs)4 Ge(C,Hs), (C. Winkler, 1887) d=0.96 d=0.99 Sn(C;Hs)4 bp: 160°C bp: 163.5°C L. Mond: Ni(CO),, first binary metal carbonyl, used in a commercial process for refining nickel. Mond is the founder of the English company ICI (Imperial Chem- ical Industries) as well as a renowned collector and patron of the arts. P. Barbier replaces Mg for Zn in reactions with alkyl iodides: H,C. oO H,C. a Sc=cH-cH,-c0 EGEEMS," So—cH-CH,-C-CH, H,C CH,” H,C cu 3 explored in more detail by Barbier’s student V. Grignard (Nobel prize 1912 shared with P. Sabatier). Although less sensitive than ZnR,, RMgxX is a more potent alkyl group transfer reagent. L. F. S. Kipping prepares (C.Hs),SiO, suspects its high molecularity, and calls the material diphenylsilicone. W. J. Pope: formation of (CH;)3Ptl, first o-organotransition-metal compound. P. Ehrlich (inventor of chemotherapy, Nobel prize 1908) introduces Salvarsan for the treatment of syphilis. W. Schlenk: Lithium alkyls via transalkylation. 2Li + R,ZHg ———> 2 LiR + Hg 2 BtLi + Me,Hg ——> 2 MeLi + Et,Hg1 Historical Development and Current Trends in Organometallic Chemistry 3 1919 1922 1928 1929 1930 19314 1938 1939 1943 1951 1953 1955 1955 1956 1959 F. Hein from CrCl, and PhMgBr synthesizes polyphenylchromium compounds, now known to be sandwich complexes. T. Midgley and T. A. Boyd introduce Pb(C,H;), as an antiknock additive in gasoline. W. Hieber inaugurates his systematic study of metal carbonyls: Fe(CO), + H;NCH,CH,NH, —— (H,NCH,CH,NH,)Fe(CO); + 2CO Fe(CO), + XK; ——> Fe(CO),X, + 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 + 2 Li—» 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. O. Roelen discovers hydroformylation (the oxo process). W. Reppe starts work on the transition-metal catalyzed reactions of acetylenes. E. G. Rochow: 2 CHCl + Si 2%", (CH,),SICI, +... This “direct synthesis” triggers large scale production and use of silicones. Prelim- inary work by R. Miiller (Radebeul near Dresden) was interrupted by the Second World War. P. Pauson (GB) and S. A. Miller (USA) obtain ferrocene (C5H;),Fe, first sand- wich complex. G. Wittig discovers the reaction bearing his name. E. O. Fischer: rational synthesis of bis(benzene)chromium (CgH,)Cr. K. Ziegler, G. Natta: polyolefins from ethylene and propylene, respectively, in a low pressure process employing mixed metal catalysts (transition-metal halide/ AIR;). H. C. Brown: hydroboration. J. Smidt, W. Hafner: preparation of [(C3H,)PdCl],, installation of the field of n-allyl transition-metal complexes.4 1 Historical Development and Current Trends in Organometallic Chemistry 1959 R. Criegee: stabilization of cyclobutadiene by complexation in [(C,Me,)NiCl,], verifying a prediction by H. C. Longuet-Higgins and L. Orgel (1956). 1960 M. F. Hawthorne: carboranes. 1961 L. Vaska: (PPh3)2Ir(CO)CI reversibly binds O,. 1963 Nobel prize to K. Ziegler and G. Natta. 1964 E. O. Fischer: (CO);WC(OMe)Me, first carbene complex. 1965 G. Wilkinson, R. S. Coffey: (PPh;),RhCl acts as a homogeneous catalyst in the * hydrogenation of alkenes. 1968 A. Streitwieser: preparation of uranocene, (CgsH,).U. 1969 P. L. Timms: synthesis of organotransition-metal complexes by means of metal- atom ligand-vapor cocondensation. 1970 G. Wilkinson: kinetically inert transition-metal alkyls through blockage of f-elim- ination. 1972 H. Werner: [((CsH;)3Ni,]*, first triple-decker sandwich complex. 1973 E. O. Fischer: I(CO),Cr(CR), first carbyne complex. 1973 Nobel prize to E. O. Fischer and G. Wilkinson. 1976 Nobel prize to W. N. Lipscomb: theoretical and experimental clarification of structure and bonding in boranes. 1979 Nobel prize to H. C. Brown and G. Wittig: applications of organoboranes and methylenephosphoranes, respectively, in organic synthesis. 1981 R. West: (1,3,5-MesCH,),Si2, first stable compound with a ~Si=Si_ double bond. 1981 Nobel prize to R. Hoffmann and K. Fukui: semiempirical MO-concepts in a uni- fied discussion of structure and reactivity of inorganic, organic and organometallic molecules, isolobal analogies. 1983 R. G. Bergman, W. A. G. Graham: intermolecular reactions of organotransition- metal compounds with alkanes (C —H activation). 51 Historical Development and Current Trends in Organometallic Chemistry 5 Current Trends @ Participation of higher main-group elements in p,—p, multiple bonds Examples: R Ar | > nC pen Sp= se 2 a si Ar 1 R H Siline, accessible in the gasphase Arsaalkyne Distibene and in matrix isolation R=t-Bu Ar=1,3,5-(-Bu);CgH, @ Stabilization of highly reactive species by metal coordination Examples: cyclobutadiene, aryne, carbyne, thiocarbonyl, selenoformaldchyde. LS PPhg Fe (megCO)gW =C—M Cn 9 pe “fe jegCO)3W =C—Me 0s—y aoEiN oc” | CH; oc co ~CO PPhg 7 @® Metallacycles ——————+ VoGH LOH Examples: (AgCl) (CR)Os(CO) (PR3)2Cl Cp,W—CH,—CH,—CH, QB, & @ Study of organometallic clusters Example: [Me;NCH,Ph],[Ni3sPt.(CO),3H] Metal skeleton of the cluster anion Electron micrograph (X-ray diffraction) of the supported material6 1 Historical Development and Current Trends in Organometallic Chemistry © Catalysis via organometallic intermediates Examples of industrial processes: technical improvements in the hydroformylation reac- tion (oxo process), developments in the areas of Fischer-Tropsch chemistry, alkene metathesis and C—H activation. Example of an organic synthesis: PdL,-catalyzed enantioselective allylic alkylation (transfer of chirality). 9 R, H RR 95% diastereomeric purity: eh AX R © profits from fundamental work carried out on the topics Q@-@. Production figures of organometallic compounds; 1. Silicones 700000 t/a 2. Pb-alkyls 600000 t/a (declining) 3. Organo-Al 50000 t/a 4. Organo-Sn 35000 t/a 5. Organo-Li 900 t/a Even more impressive than the figures for main-group organometallics is the volume of organic intermediates and of polymers which are produced through the use of organo- transition-metal catalysis: 1. Polypropylene 7.7 10° t/a 2. “Oxo products” 5.0.x 10° t/a 3. Acetaldehyde 2.2.x 10° t/a 4. Acetic acid 1.0 x 10° t/a2, Demarcation and Classification of Organometallic Compounds Organometallic compounds (metal organyls, organometallics) are defined as materials which possess direct, more or less polar bonds M’* — C’~ between metal and carbon 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 organometallics is based on the bond type: 1 covalent, 18 multicenter bonds 2 13 14 15 16 17] He 4 5 6 7 8 9 10 11 Ti V Cr Mn Fe Co Ni Cu]Zn Ga Ge As Se] Br Kr Zr Nb Mo Te Ru Rh Pd Ag]Cd In Sn Sb Te] I Xe La¥ Hf Ta W Re Os Ir Pt AulHg TI Pb Bi Pol|At Rn covalent { covalent ionic M~C o-bonds mainly E—C o-bonds as well as M—C 7-bonds rarely E—C rmbonds & Lanthanoids ionic ‘& Actinoids M=C bond predominantly covatent8 2 Demarcation and Classification of Organometallic Compounds The designation o-, x-, 5-bond is defined as follows: Overlap Number of nodal Planes Bond Example including the Bond Axis Type Pb) + 2CHoq) AH =—307 kJ/mol (1) Factors which contribute to the driving force of this reaction include the enthalpy of formation AH? (C,H,y) of the product as well as an entropy term AS > 0. Besides reaction (1), additional reaction paths have been established for the thermolysis of tetramethyl- lead: Pb(CH3)ai) —> Pg) + 2CHay + C2Hag) AH = — 235 kJ/mol (2) P(CH3)aig) —> Pb) + 2H +2C2Hy AH =— 33kJ/mol (3) The appearance of ethylene in the product mixture suggests that homolytic cleavage R3M—R ——> {R3M’ + R'} —> products (4) is accompanied by f-elimination a 8B 7 COR RgC—CR meta ine ary et M—H + RoC =CRy (5) M’H M--H3.2. Lability of Main-group Organometallics 13 . The concerted nature of decomposition pathway (5) entails a lowering of the activation * gy, However, this path is limited to molecules with hydrogen atoms in B-position. It is plausible, therefore, that the temperature of decomposition is higher for Po(CH;), than for Pb(C2Hs)4 (p. 139). +4 ; = A further condition for B-climination to occur is the availability of an empty valence orbital on M to interact with the electron pair of the C;—H bond. It is for this reason that the B-elimination mechanism plays a more important role for the organometallics of groups 1, 2 and 13 (valence configurations s', s? and s? p') than for those of groups 14, 45 and 16 (s? p?, sp? and s? p*). Ifa binary organometallic species has an empty coordi- nation site at its disposal, B-e imination can be blocked and thermal stability increased through formation of a Lewis base adduct (Example: (bipy)Be(C,H;),, bipy = 2,2’- bipyridyl]. B-Elimination assumes a position of prime importance in the chemistry of organotransition-metal compounds (chapter 13). As with organic compounds, all organometallic materials are thermodynamically un- stable with respect to oxidation to MO,, H,O and CO). Nevertheless, Jarge differences in the ease of handling of organometallics are encountered which may be traced back to differences in kinetic intertness. Example: Heat of Thermo- Property Kinetics combustion dynamics Zn(C,Hs)2 ~1920 kJ/mol unstable pyrophoric labile Sn(CH,). —3590 kJ/mol unstable airstable inert Particularly labile against O, and H,O are organometallic molecules which possess free electron pairs, low lying empty orbitals and/or high polarity of the M—C bonds. Com- pare: In air: In water: Relevant factors: Me,In pyrophoric hydrolysed electron gap at In, high bond polarity. Me,Sn inert inert Sn shielded well, low bond polarity. Me3Sb pyrophoric inert free electron pair on Sb. Me3B pyrophoric inert electron gap at B is closed by means of hyperconjugation, low bond polarity. Me, Al pyrophoric hydrolysed electron gap at Al in the monomer, nucleophilic attack via Al(3d) in the dimer, high bond polarity. SiH, pyrophoric hydrolysed Si shielded ineffectively, attack of O, . and of nucleophiles via Si(3d). SiCL, inert hydrolysed Si relatively electron-poor, high polarity of SiC bonds, nucleophilic attack via Si(3d). SiMe, inert inert Si shielded effectively, low polarity of Si—C bonds. This brief survey is only intended to furnish a few qualitative arguments which haye to weighed with respect to their specific applications.