Organometallic Chemistry and Catalysis

598 Pages·2007·35.38 MB·English

by  Didier Astruc (auth.)

ATOMIC WEIGHTS OF THE ELEMENTS a, b
(adapted from T.B. Coplen et al., Inorg. Chim. Acta 217, 217, 1994)
Element Symbol Atomic Atomic Element Symbol Atomic Atomic
Number Weight Number Weight
Actiniumc 227Ac 89 227.03 Mercury Hg 80 200.59(2)
Aluminum Al 13 26.982 Molybdenum Mo 42 95.94
Americiumc Am 95 241.06 Neodynium Nd 60 144.24(3)
Antimony Sb 51 121.76 Neon Ne 10 20.180
Argon Ar 18 39.948 Neptuniumc 237Np 93 237.05
Arsenic As 33 74.922 Nickel Ni 28 58.693
Astatinec 210At 85 209.99 Niobium Nb 41 92.906
Barium Ba 56 137.33 Nitrogen N 7 14.007
Berkeliumc 249Bk 97 249.08 Nobeliumc 259No 102 259.10
Beryllium Be 4 9.0122 Osmium Os 76 190.23(3)
Bismuth Bi 83 208.98 Oxygen O 8 15.999
Boron B 5 10.811(5) Palladium Pd 46 106.42
Bromine Br 35 79.904 Phosphorus P 15 30.974
Cadmium Cd 48 112.41 Platinum Pt 78 195.08(3)
Calcium Ca 20 40.078(4) Plutoniumc 239Pu 94 239.05
Californiumc 232Cf 98 252.08 Poloniumc 210Po 84 209.98
Carbon C 6 12.011 Potassium K 19 39.098
Cerium Ce 58 140.12 Praseodynium Pr 59 140.91
Cesium Cs 55 132.91 Promethiumc 147Pm 61 146.92
Chlorine Cl 17 35.453 Proactiniumc Pa 91 231.04
Chromium Cr 24 51.996 Radiumc 226Ra 88 226.03
Cobalt Co 27 58.933 Radonc 222Rn 86 222.02
Copper Cu 29 63.546(3) Rhenium Re 75 186.21
Curiumc 244Cm 96 244.06 Rhodium Rh 45 102.91
Dysprosiumc Dy 66 162.50(3) Rubidium Rb 37 85.468
Einsteiniumc 252Es 99 252.08 Ruthenium Ru 44 101.07(2)
Erbium Er 68 167.26(3) Samarium Sm 62 150.36(3)
Europium Eu 63 151.96 Scandium Sc 21 44.956
Fermiumc 257Fm 100 257.1 Selenium Se 34 78.96(3)
Fluorine F 9 18.998 Silicon Si 14 28.086
Franciumc 223Fr 87 223.02 Silver Ag 47 107.87
Gadolinium Gd 64 157.25(3) Sodium Na 11 22.990
Gallium Ga 31 69.723 Strontium Sr 38 87.62
Germanium Ge 32 72.61(2) Sulfur S 16 32.066(6)
Gold Au 79 196.97 Tantalum Ta 73 180.95
Hafnium Hf 72 178.49(2) Technetiumc 99Tc 43 98.906
Helium He 2 4.0026 Tellurium Te 52 127.60(3)
Holmium Ho 67 164.93 Terbium Tb 65 158.93
Hydrogen H 1 1.0079 Thallium Tl 81 204.38
Indium In 49 114.82 Thoriumc Th 90 232.04
Iodine I 53 126.9 Thulium Tm 69 168.93
Iridium Ir 77 192.22 Tin Sn 50 118.71
Iron Fe 26 55.845(2) Titanium Ti 22 47.867
Krypton Kr 36 83.8 Tunsgten W 74 183.84
Lanthanum La 57 138.91 Uraniumc U 92 238.03
Lawrenciumc 262Lw 103 262.11 Vanadium V 23 50.942
Lead Pb 82 207.02 Xenon Xe 54 131.29(2)
Lithium Li 3 [6.941(2)]b Ytterbium Yb 70 173.04(3)
Luteciumc Lu 71 174.97 Yttrium Y 39 88.906
Magnesium Mg 12 24.305 Zinc Zn 30 65.39(2)
Manganese Mn 25 54.938 Zirconium Zr 40 91.224(2)
Mendeleviumc 258Mv 101 258.1
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.
DidierAstruc
OrganometallicChemistryandCatalysis
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“OrganometallicChemistryandCatalysis”isanimprovedversionoftheFrenchbookpublished
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RobertCorriu,MemberoftheFrenchAcademyofScienceandtheFrenchUniversityInstitute,
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Jean-Ren´eHamon,SeniorResearcherattheCNRS,UniversityofRennes
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BernardWaegell,professorattheUniversityofAix-Marseille
Didier Astruc
Organometallic Chemistry
and Catalysis
With860Figuresand27Tables
123
DidierAstruc
MemberoftheInstitutUniversitairedeFrance
InstitutdesSciencesMol´eculaires,GroupeNanosciencesMol´eculairesetCatalyse
◦
UMRCNRSN 5255
Universit´eBordeauxI
351,CoursdelaLib´eration
33405TalenceCedex
France
email:[email protected]
OriginallypublishedinFrench:DidierAstruc,ChimieOrganom´etallique,EDPSciences,
Grenoble2000,ISBN978-2-86883-493-5
LibraryofCongressControlNumber:2007924912
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P
REFACE
This text is a translation and thorough revision of the French book “Chimie
Organométallique” that was published by EDP Sciences in 2000 and whose Spanish
version, prepared by Carmen Claver and Beatriz Alonso, was published by Reverte
in 2003. The catalysis part has been considerably extended, however. Not only has
it been re-organized and complemented, but new chapters have been written on
homogeneous 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 general
advice, 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 their
editorial efforts as well as Sylvie Bordage (Grenoble Sciences) for her superb work
in the book production and Theodor C.H. Cole (Springer) for excellent copy-editing.
Didier ASTRUC,
Talence, February 2007
C
ONTENTS
Introduction..........................................................................................................1
1. Organization of the text......................................................................................1
2. Frontiers of organometallic chemistry................................................................2
3. Situation of the book with respect to teaching....................................................2
4. Reference books and other selected references...................................................3
History of organometallic chemistry...................................................................5
1760-1900:The first complexes..............................................................................5
1900-1950:Grignard, Sabatier, and catalysis in Germany.......................................6
1950-1960:The discovery of ferrocene and the boom of organometallic chemistry.7
1961-1981:The discovery of multiple metal-carbon bonds
and the golden age of catalysis.............................................................9
1970-1985:Activation of C-H bonds in hydrocarbons,
(cid:2)-bond metathesis and H as a ligand.................................................16
2
Current trends.......................................................................................................18
PART I
STRUCTURES OF THE TRANSITION-METAL COMPLEXES
Chapter 1 - Monometallic transition-metal complexes.....................................23
1. The ligands......................................................................................................23
2. The characteristics of the transition-metal in the complexes.............................32
3. Hapticity of the ligands and linear writing of the complex formulas.................36
4. The “18-electron rule”: tendencies and exceptions...........................................37
5. Bonding between the transition metal and the (cid:1)-acceptor (CO, C H )
2 4
and (cid:1)-donor ligands (halogeno, alkoxy, amino)................................................41
6. Molecular orbital diagrams.............................................................................44
Summary and Exercises........................................................................................45
Chapter 2 - Bimetallic transition-metal complexes and clusters......................47
1. The metal-metal bond in bimetallic complexes................................................48
Types of molecular magnetism........................................................................59
2. Clusters............................................................................................................60
3. The isolobal analogy........................................................................................73
Summary and Exercises........................................................................................76
VIII ORGANOMETALLIC CHEMISTRY AND CATALYSIS
PART II
THE STOICHIOMETRIC REACTIONS OF TRANSITION-METAL COMPLEXES
Chapter 3 - Redox reactions, oxidative addition and (cid:4)-bond metathesis.........81
1. Outer-sphere electron transfer..........................................................................81
2. Inner-sphere electron- and atom transfer..........................................................85
3. Oxidative addition, reductive elimination and (cid:4)-bond metathesis.....................87
Summary and Exercises.......................................................................................106
Chapter 4 - Reactions of nucleophiles and electrophiles with complexes........109
1. Nucleophilic reactions....................................................................................109
2. Reactions of electrophiles...............................................................................115
Summary and Exercises.......................................................................................119
Chapter 5 - Ligand substitution reactions........................................................121
1. Introduction....................................................................................................121
2. “Pairwise” mechanisms...................................................................................121
3. Electron-transfer-chain and atom-transfer-chain mechanisms..........................127
4. Substitution of XL ligands (n = 0-2)..............................................................132
n
Summary and Exercises.......................................................................................133
Chapter 6 - Insertion and extrusion reactions..................................................135
1. Introduction....................................................................................................135
2. CO 1,1 migratory insertion.............................................................................136
3. Methylene insertion and extrusion..................................................................139
4. 1, 2 migratory insertion of alkenes and alkynes into M-H bonds......................140
5. Insertion of alkenes into metal-alkyl bonds and the reverse reaction:
C-C activation by (cid:2)-alkyl elimination.............................................................142
6. (cid:1) and (cid:3)-elimination.........................................................................................143
Summary and Exercises.......................................................................................146
PART III
THE MAIN FAMILIES OF ORGANOMETALLIC COMPLEXES
Chapter 7 - Metal carbonyls and complexes of other monohapto L ligands...151
1. Introduction....................................................................................................151
2. Syntheses........................................................................................................152
3. Binding modes................................................................................................153
4. Reactions........................................................................................................159
5. Ligands isoelectronic to CO: CNR, CS, CSe, N and NO+...............................162
2
6. Dioxygen O ...................................................................................................168
2
7. Phosphanes.....................................................................................................168
8. Weak L ligands and their role to generate organometallic Lewis acids............171
Summary and Exercises.......................................................................................172
CONTENTS IX
Chapter 8 - Metal-alkyl and -hydride complexes
and other complexes of monohapto X ligands..................................................175
1. Different types of sp(cid:1)3 metal-carbon bonds......................................................175
2. Stability of metal-alkyl complexes..................................................................175
3. Synthesis of metal-alkyl complexes................................................................179
4. Properties of metal-alkyl complexes................................................................180
5. Metallocycles..................................................................................................181
6. Metal-aryl, -vinyl, -alkynyl, -silyl, and -stannyl complexes.............................182
7. Metal-hydrides and the dihydrogen ligand......................................................184
8. Alkoxy and amido complexes.........................................................................193
Summary and Exercises.......................................................................................194
Chapter 9 - Metal-carbene and -carbyne complexes
and multiple bonds with transition metals.......................................................197
1. Metal-carbene complexes................................................................................197
2. Metal-carbyne complexes...............................................................................215
3. Multiple bond between a heteroatom and a transition metal:
oxo, imido, phosphinidene and nitrido ligands................................................217
Summary and Exercises.......................................................................................223
Chapter 10 - (cid:1) complexes of mono- and polyenes and enyls............................225
1. Metal-olefin complexes...................................................................................225
2. Metal-diene complexes and analogues............................................................228
3. Metal-alkyne complexes.................................................................................231
4. (cid:1)-Allyl complexes..........................................................................................233
5. Polyenyl complexes........................................................................................237
6. Arene complexes............................................................................................242
Summary and Exercises.......................................................................................248
Chapter 11 - Metallocenes and sandwich complexes.......................................251
1. Structure of the metallocenes..........................................................................251
2. Redox properties of the sandwich metallocenes..............................................255
3. Metallocene synthesis.....................................................................................256
4. Chemical properties of metallocenes...............................................................258
5. Triple- and multiple-decker sandwich complexes............................................266
6. Non-sandwich metallocenes derivatives..........................................................268
7. Metal-bis-arene sandwich complexes..............................................................270
8. Cylopentadienyl-metal-arene complexes.........................................................274
Summary and Exercises.......................................................................................287