ATOMIC WEIGHTS OF THE ELEMENTS a, b

(adapted from T.B. Coplen et al., Inorg. Chim. Acta 217, 217, 1994)

Actiniumc

AluminumAmericiumc

AntimonyArgonArsenicAstatinec

BariumBerkeliumc

BerylliumBismuthBoronBromineCadmiumCalciumCaliforniumc

CarbonCeriumCesiumChlorineChromiumCobaltCopperCuriumc

Dysprosiumc

Einsteiniumc

ErbiumEuropiumFermiumc

FluorineFranciumc

GadoliniumGalliumGermaniumGoldHafniumHeliumHolmiumHydrogenIndiumIodineIridiumIronKryptonLanthanumLawrenciumc

LeadLithiumLuteciumc

MagnesiumManganeseMendeleviumc

227Ac Al Am Sb Ar As210At Ba249Bk Be Bi B Br Cd Ca232Cf C Ce Cs Cl Cr Co Cu244Cm Dy252Es Er Eu257Fm F223Fr Gd Ga Ge Au Hf He Ho H In I Ir Fe Kr La262Lw Pb Li Lu Mg Mn258Mv

MercuryMolybdenumNeodyniumNeonNeptuniumc

NickelNiobiumNitrogenNobeliumc

OsmiumOxygenPalladiumPhosphorusPlatinumPlutoniumc

Poloniumc

PotassiumPraseodyniumPromethiumc

Proactiniumc

Radiumc

Radonc

RheniumRhodiumRubidiumRutheniumSamariumScandiumSeleniumSiliconSilverSodiumStrontiumSulfurTantalumTechnetiumc

TelluriumTerbiumThalliumThoriumc

ThuliumTinTitaniumTunsgtenUraniumc

VanadiumXenonYtterbiumYttriumZincZirconium

Hg Mo Nd Ne237Np Ni Nb N259No Os O Pd P Pt239Pu210Po K Pr147Pm Pa226Ra222Rn Re Rh Rb Ru Sm Sc Se Si Ag Na Sr S Ta 99Tc Te Tb Tl Th Tm Sn Ti W U V Xe Yb Y Zn Zr

8913955118338556974

835

354820986

5855172427299666996863

1009

8764313279722

671

495377263657

103823

711225

101

804260109328417

102768

46157894841959619188867545374462213414471138167343526581906950227492235470393040

227.03 26.982

241.06121.76

39.948 74.922

209.99137.33249.08

9.0122208.98

10.811(5) 79.904

112.41 40.078(4)

252.08 12.011

140.12132.91

35.453 51.996 58.933

63.546(3)244.06

162.50(3)252.08

167.26(3)151.96257.1

18.998223.02

157.25(3) 69.723

72.61(2)196.97

178.49(2) 4.0026

164.93 1.0079

114.82126.9

192.22 55.845(2)

83.8138.91262.11207.02

[6.941(2)]b

174.97 24.305

54.938 258.1

200.59(2) 95.94

144.24(3) 20.180

237.05 58.693 92.906 14.007

259.10 190.23(3)

15.999106.42

30.974 195.08(3)

239.05209.98

39.098140.91146.92231.04226.03222.02186.21102.91

85.468 101.07(2) 150.36(3)

44.956 78.96(3)

28.086107.87

22.990 87.62

32.066(6)180.95

98.906 127.60(3)

158.93204.38232.04168.93118.71

47.867183.84238.03

50.942 131.29(2) 173.04(3)

88.906 65.39(2)

91.224(2)

Element Symbol Element SymbolAtomicNumber

AtomicNumber

AtomicWeight

AtomicWeight

a : based on a mass for 12C of 12.000.b : given five significant digits; if less, the errors are given in parentheses after the atomic mass. c : indicates the most known isotope for artificial elements.

Didier Astruc

Organometallic Chemistry and Catalysis

Grenoble Sciences

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Grenoble Sciences is supported by the French Ministry of Education and Research and the“Region Rhone-Alpes”.

“Organometallic Chemistry and Catalysis” is an improved version of the French book publishedby Grenoble Sciences in partnership with EDP Sciences. The Reading Committee of the Frenchversion included the following members:

Yves Chauvin, Nobel prizewinner (2005), Honorary Scientific Director of the French PetrolInstitute,

Robert Corriu, Member of the French Academy of Science and the French University Institute,professor at the University of Montpellier,

Jean-Rene Hamon, Senior Researcher at the CNRS, University of Rennes

Henri Kagan, Member of the French Academy of Science and the French University Institute,professor at he University of Paris-Sud, Orsay,

Paul Knochel, Professor at the Ludwig Maximilians Universitat, Munchen,

Bernard Meunier, Member of the French Academy of Science, Senior researcher at the CNRSin Toulouse,

Jean-Francois Normant, Member of the French Academy of Science, professor at the Pierre etMarie Curie University, Paris

Jean-Yves Saillard, professor at the University of Rennes

Jean-Pierre Sauvage, Member of the French Academy of Science, Senior researcher at theCNRS in Strasbourg,

Bernard Waegell, professor at the University of Aix-Marseille

Didier Astruc

Organometallic Chemistryand Catalysis

With 860 Figures and 27 Tables

123

Didier AstrucMember of the Institut Universitaire de FranceInstitut des Sciences Moleculaires, Groupe Nanosciences Moleculaires et CatalyseUMR CNRS N◦ 5255Universite Bordeaux I351, Cours de la Liberation33405 Talence CedexFranceemail: d.astruc@ism.u-bordeaux1.fr

Originally published in French: Didier Astruc, Chimie Organometallique, EDP Sciences,Grenoble 2000, ISBN 978-2-86883-493-5

Library of Congress Control Number: 2007924912

ISBN 978-3-540-46128-9 Springer Berlin Heidelberg New YorkDOI 10.1007/978-3-540-46129-6

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E. Alonso, D. Astruc – Introduction of the Cluster Fragment Ru3(CO)11 at the periphery of PhosphineDendrimers Catalyzed by the Electron-Reservoir Complex [FeI Cp(C6Me6)], J. Am. Chem. Soc. 2000,122, 3222

Printed on acid-free paper 2/3180/YL 5 4 3 2 1 0

PREFACE

This text is a translation and thorough revision of the French book “ChimieOrganométallique” that was published by EDP Sciences in 2000 and whose Spanishversion, prepared by Carmen Claver and Beatriz Alonso, was published by Revertein 2003. The catalysis part has been considerably extended, however. Not only hasit been re-organized and complemented, but new chapters have been written onhomogeneous catalytic hydrocarbon activation and on heterogeneous catalysis.

I would like to thank the colleagues who have corrected parts of the French Edition:Yves Chauvin (IFP and Villeurbanne) for the catalysis section, Jean-René Hamon(Rennes) who read the entire French version, Catherine Hemmert (LCC, Toulouse),who corrected the enzymatic catalysis chapter, Henri Kagan (Orsay) for generaladvice, Jean-Yves Saillard (Rennes) for the theoretical aspects and Bernard Waegel(Marseille) for remarks on the catalysis chapters. I am grateful to Alan H. Cowley(U.T. Austin), Andrew Wojcicki (Columbus), Jonathan Egbert and Travis J. Ebden(Seattle) for proofreading several chapters of the English text and to Cátia Ornelas(Talence) for proofreading the entire book.

Finally, it is a great pleasure to thank Jean Bornarel and Nicole Sauval for theireditorial efforts as well as Sylvie Bordage (Grenoble Sciences) for her superb workin the book production and Theodor C.H. Cole (Springer) for excellent copy-editing.

Didier ASTRUC,

Talence, February 2007

CONTENTS

Introduction.......................................................................................................... 11. Organization of the text...................................................................................... 12. Frontiers of organometallic chemistry ................................................................ 23. Situation of the book with respect to teaching .................................................... 24. Reference books and other selected references ................................................... 3

History of organometallic chemistry ................................................................... 51760-1900: The first complexes .............................................................................. 51900-1950: Grignard, Sabatier, and catalysis in Germany ....................................... 61950-1960: The discovery of ferrocene and the boom of organometallic chemistry. 71961-1981: The discovery of multiple metal-carbon bonds

and the golden age of catalysis ............................................................. 91970-1985: Activation of C-H bonds in hydrocarbons,

-bond metathesis and H2 as a ligand ................................................. 16Current trends....................................................................................................... 18

PART ISTRUCTURES OF THE TRANSITION-METAL COMPLEXES

Chapter 1 - Monometallic transition-metal complexes ..................................... 231. The ligands ...................................................................................................... 232. The characteristics of the transition-metal in the complexes ............................. 323. Hapticity of the ligands and linear writing of the complex formulas ................. 364. The “18-electron rule”: tendencies and exceptions ........................................... 375. Bonding between the transition metal and the -acceptor (CO, C2H4)

and -donor ligands (halogeno, alkoxy, amino)................................................ 416. Molecular orbital diagrams ............................................................................. 44Summary and Exercises........................................................................................ 45

Chapter 2 - Bimetallic transition-metal complexes and clusters ...................... 471. The metal-metal bond in bimetallic complexes ................................................ 48

Types of molecular magnetism ........................................................................ 592. Clusters............................................................................................................ 603. The isolobal analogy........................................................................................ 73Summary and Exercises........................................................................................ 76

VIII ORGANOMETALLIC CHEMISTRY AND CATALYSIS

PART IITHE STOICHIOMETRIC REACTIONS OF TRANSITION-METAL COMPLEXES

Chapter 3 - Redox reactions, oxidative addition and -bond metathesis......... 811. Outer-sphere electron transfer .......................................................................... 812. Inner-sphere electron- and atom transfer .......................................................... 853. Oxidative addition, reductive elimination and -bond metathesis..................... 87Summary and Exercises.......................................................................................106

Chapter 4 - Reactions of nucleophiles and electrophiles with complexes........1091. Nucleophilic reactions ....................................................................................1092. Reactions of electrophiles ...............................................................................115Summary and Exercises.......................................................................................119

Chapter 5 - Ligand substitution reactions........................................................1211. Introduction ....................................................................................................1212. “Pairwise” mechanisms...................................................................................1213. Electron-transfer-chain and atom-transfer-chain mechanisms..........................1274. Substitution of XLn ligands (n = 0-2) ..............................................................132Summary and Exercises.......................................................................................133

Chapter 6 - Insertion and extrusion reactions..................................................1351. Introduction ....................................................................................................1352. CO 1,1 migratory insertion .............................................................................1363. Methylene insertion and extrusion ..................................................................1394. 1, 2 migratory insertion of alkenes and alkynes into M-H bonds......................1405. Insertion of alkenes into metal-alkyl bonds and the reverse reaction:

C-C activation by -alkyl elimination .............................................................1426. and -elimination.........................................................................................143Summary and Exercises.......................................................................................146

PART IIITHE MAIN FAMILIES OF ORGANOMETALLIC COMPLEXES

Chapter 7 - Metal carbonyls and complexes of other monohapto L ligands...1511. Introduction ....................................................................................................1512. Syntheses........................................................................................................1523. Binding modes................................................................................................1534. Reactions ........................................................................................................1595. Ligands isoelectronic to CO: CNR, CS, CSe, N2 and NO+...............................1626. Dioxygen O2 ...................................................................................................1687. Phosphanes .....................................................................................................1688. Weak L ligands and their role to generate organometallic Lewis acids ............171Summary and Exercises.......................................................................................172

CONTENTS IX

Chapter 8 - Metal-alkyl and -hydride complexesand other complexes of monohapto X ligands..................................................1751. Different types of sp 3 metal-carbon bonds ......................................................1752. Stability of metal-alkyl complexes ..................................................................1753. Synthesis of metal-alkyl complexes ................................................................1794. Properties of metal-alkyl complexes................................................................1805. Metallocycles..................................................................................................1816. Metal-aryl, -vinyl, -alkynyl, -silyl, and -stannyl complexes .............................1827. Metal-hydrides and the dihydrogen ligand ......................................................1848. Alkoxy and amido complexes .........................................................................193Summary and Exercises.......................................................................................194

Chapter 9 - Metal-carbene and -carbyne complexesand multiple bonds with transition metals .......................................................1971. Metal-carbene complexes................................................................................1972. Metal-carbyne complexes ...............................................................................2153. Multiple bond between a heteroatom and a transition metal:

oxo, imido, phosphinidene and nitrido ligands ................................................217Summary and Exercises.......................................................................................223

Chapter 10 - complexes of mono- and polyenes and enyls............................2251. Metal-olefin complexes...................................................................................2252. Metal-diene complexes and analogues ............................................................2283. Metal-alkyne complexes .................................................................................2314. -Allyl complexes ..........................................................................................2335. Polyenyl complexes ........................................................................................2376. Arene complexes ............................................................................................242Summary and Exercises.......................................................................................248

Chapter 11 - Metallocenes and sandwich complexes .......................................2511. Structure of the metallocenes ..........................................................................2512. Redox properties of the sandwich metallocenes ..............................................2553. Metallocene synthesis .....................................................................................2564. Chemical properties of metallocenes...............................................................2585. Triple- and multiple-decker sandwich complexes............................................2666. Non-sandwich metallocenes derivatives..........................................................2687. Metal-bis-arene sandwich complexes..............................................................2708. Cylopentadienyl-metal-arene complexes.........................................................274Summary and Exercises.......................................................................................287

X ORGANOMETALLIC CHEMISTRY AND CATALYSIS

Chapter 12 - Ionic and polar metal-carbon bonds:alkali and rare-earth complexes .......................................................................2891. Introduction ....................................................................................................2892. Organometallic complexes of alkali metals .....................................................2893. Grignard reagents ...........................................................................................2934. The scandium, ytrium, lanthanides and actinides complexes ...........................296Summary and Exercises.......................................................................................310

Chapter 13 - Covalent chemistry of the organoelementsof frontier (11, 12) and main (13-16) groups ....................................................3131. Introduction ....................................................................................................3132. Group 11 (Cu, Ag, Au) ...................................................................................3143. Group 12 (Zn, Cd, Hg)....................................................................................3164. Group 13 (B, Al, Ga, In, Tl)............................................................................3205. Group 14 (Si, Ge, Sn, Pb) ...............................................................................3286. Group 15 (As, Sb, Bi) .....................................................................................3407. Group 16 (Se, Te) ...........................................................................................344Summary and Exercises.......................................................................................346

PART IVCATALYSIS

Introduction to catalysis....................................................................................351

Chapter 14 - Hydrogenation and hydroelementation of alkenes.....................3571. Hydrogenation of olefins ................................................................................3572. Asymmetric hydrogenation .............................................................................3604. Hydroboration of olefins .................................................................................3625. Hydrocyanation of olefins...............................................................................3626. Hydroamination of olefins and alkynes ...........................................................363Summary and Exercises.......................................................................................364

Chapter 15 - Transformations of alkenes and alkynes ....................................3671. Ziegler-Natta-type olefin polymerization ........................................................3672. Metathesis of alkenes, alkynes and cycloalkenes.............................................3733. Olefin dimerization and oligomerization .........................................................3864. Olefin isomerization .......................................................................................390Summary and Exercises.......................................................................................392

CONTENTS XI

Chapter 16 - Oxidation of olefins......................................................................3951. Historic introduction and radical-type oxidation..............................................3952. Ethylene oxidation to acetaldehyde: Wacker process.......................................3964. Epoxidation of olefins.....................................................................................3995. Hydroxylation by metal-oxo complexes ..........................................................4026. Phase-transfer catalysis in oxidation chemistry ...............................................405Summary and Exercises.......................................................................................407

Chapter 17 - C-H activation and functionalization of alkanes and arenes......4091. Introduction ....................................................................................................4092. Alkanes and cycloalkanes ...............................................................................4103. Aromatics .......................................................................................................419Summary and Exercises.......................................................................................428

Chapter 18 - Carbonylation and carboxylation reactions ...............................4311. Carbonylation of methanol: Monsanto process................................................4312. Olefin hydroformylation: oxo process .............................................................4333. Carbonylation of alkenes and alkynes in the presence of a nucleophile:

the Reppe reaction ..........................................................................................4344. Carbonylation of aryl halides in the presence of a nucleophile ........................4365. Catalysis of CO2 transformation......................................................................437Summary and Exercises.......................................................................................438

Chapter 19 - Bio-organometallic chemistry: enzymatic catalysis....................4411. Introduction ....................................................................................................4412. Cobalamin: co-enzyme vitamin B12.................................................................4423. Biological redox mediators .............................................................................4454. Examples of oxido-reductase enzymes: the mono-oxygenases ........................4465. Nitrogen fixation by nitrogenase enzyme ........................................................4486. Nickel enzymes ..............................................................................................452Summary and Exercises.......................................................................................455

Chapter 20 Heterogeneous catalysis ................................................................4571. Introduction.....................................................................................................4572. Concepts of heterogeneous catalysis ................................................................4603. CO and CO2 hydrogenation and Fischer-Tropsch chemistry............................4694. Transformation of hydrocarbons......................................................................4755. Metathesis of alkanes, alkenes and alkynes......................................................4776. Oxidation of hydrocarbons ..............................................................................4807. Nanoparticle catalysis: the fast growing frontier

between homogeneous and heterogeneous catalysis ........................................483Summary and Exercises ......................................................................................485

XII ORGANOMETALLIC CHEMISTRY AND CATALYSIS

PART VAPPLICATIONS IN ORGANIC SYNTHESIS

Chapter 21 - Organometallic complexes in organic synthesisExamples of applications...................................................................................4891. Protection and stabilization of unsaturated organic derivatives and fragments .4892. Nucleophilic and electrophilic reactions on hydrocarbon ligands ....................4923. General methods of C-C bond formation

using the oxidative addition of an organic halide or a related electrophile .......4974. Extension of palladium catalysis to the formation of C-O and C-N bonds .......5165. Oxidative coupling reactions of alkynes with other unsaturated fragments

for the formation of cyclic and heterocyclic compounds..................................5186. Metal-carbene complexes in organic synthesis ................................................5217. Examples of asymmetric catalysis...................................................................523Summary and Exercises.......................................................................................530

Answers to exercises ..........................................................................................535

References..........................................................................................................553

Abbreviations ....................................................................................................591

Index ..................................................................................................................595

Atomic weights of the elements.........................................................................609

Periodic table of the elements ...........................................................................611