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Organometallic Chemistry of the Transition Elements
Florian P. Pruchnik University of Wroclaw Wroclaw, Poland
Translated from Polish by
Stan A. Duraj Cleveiand State University Cleveland, Ohio
PLENUM PRESS • NEW YORK AND LONDON
Contents
Chapter 1. Introduction to Organometallic Chemistry 1. Number of Valence Electrons. Characteristics of Ligands 1 2. The Main Group Elements 7 3. The Transition Metals 11 4. Elementary Reactions of Organometallic Compounds 15 5. Nomenclature of Organometallic Compounds 15
References 20
Chapter 2. Metal Carbonyls 1. Preparation of Metal Carbonyls .^ 23 2. Bonding in Metal Carbonyls 24 3. IR Spectra of Metal Carbonyls 32 4. Electronic Spectra 41 5. 13C NMR Spectra 45 6. Photoelectron Spectroscopy 49 7. Mass Spectrometry 53 8. Properties of Metal Carbonyls 55
a. Group 3 Metal Carbonyls 60 b. Group 4 Metal Carbonyls 63 c. Group 5 Metal Carbonyls 64 d. Group 6 Metal Carbonyls 69 e. Group 7 Metal Carbonyls 75 f. Group 8 Metal Carbonyls 79 g. Group 9 Metal Carbonyls 85
Cluster Compounds of Co, Rh, and Ir 89 h. Group 10 Metal Carbonyls 92
Metal Carbonyl Halides of Group 10 Metals 94 i. Group 11 Metal Carbonyls 95
9. Metal Carbonyl Hydrides 96 a. Bonding 96 b. Methods of Identification 97 c. Preparation of Hydrido Complexes 104
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viii Contents
d. Acidic Properties of Metal Carbonyl Hydrides 107 e. Ligand Field Strength and trans Effect of the Hydrido Ligand 107 f. Structures of Hydrido Complexes 107 g. Properties of Metal Carbonyl Hydrides 108
10. Metal Carbonyls Containing Bridging CO Groups Bonded Through C and O 110 11. Thiocarbonyl and Selenocarbonyl Complexes 112
a. Structure, Bonding, and Spectroscopy 112 b. Preparation of Thiocarbonyl and Selenocarbonyl Complexes 115 c. Reactions of Thiocarbonyl Complexes 116
12. Applications of Metal Carbonyl Complexes 119 13. Applications of Organometallic Compounds for Preparation of Metals,
Oxides, Carbides, and Nitrides, and for Deposition of Metal Layers and Their Compounds 119
14. Metal Carbonyl Complexes Possessing Column Structures 121 References 122
Chapter 3. Metal-Metal Bonds and Clusters 1. Bonding and Structure 129
a. Theory of Skeletal Electron Pairs 133 b. The Isolobal Analogy-of Fragments 141 c. Topological Calculations of CVMO 147 d. Reactions between Clusters 149 e. Molecular Orbital Theory 150
2. Clusters as Models of Metallic Lattices of Catalysts 155 3. Interstitial (Encapsulated) Clusters 157 4. "Electron Poor" Transition Metal Clusters 160 5. NMR Spectra of Clusters 163 6. IR Spectra 165 7. The M — M Bond Energy in Clusters 166 8. Synthesis of Metal Clusters 166 9. Properties of Clusters 169
a. Group 4 169 b. Group 5 170 c. Group 6 170 d. Group 7 171 e. Group 8 172 f. Group 9 174 g. Group 10 175 h. Group 11 177
10. Reactions of Clusters 179 a. Reactions Leading to Structural Changes in Clusters 180 b. Migration of Ligands Within Clusters 183 c. Acid-Base Reactions 187 d. Ligand Substitution 190 e. Oxidative Addition 190
References 193
Contents ix
Chapter 4. Compounds Containing le Carhon-Donor Ligands 1. Bonding in Compounds with Metal-Carbon a Bonds 200 2. Stability of Compounds Containing le Ligands 201 3. Structure of Compounds Containing Metal-Carbon a Bonds 208 4. IR and Raman Spectra 212 5. NMR Spectra 213 6. ESR Spectra 215 7. Photoelectron Spectra 215 8. Magnetic Properties 217 9. Electronic Spectra 218
10. Preparation of Complexes Containing a Bonded Carbon Ligands 219 a. Reactions of Transition Metal Compounds with Alkylating or Arylating
Reagents 219 b. Reactions Involving Oxidative Addition of Organic Halides 220 c. Migration (Insertion) Reactions 222 d. Reactions of Anionic Complexes with Organic Halides 224 e. Elimination of Neutral Group Connecting Carbon with Metal
(Deinsertion) 224 f. Preparation of Acetylide Complexes 225 g. Photochemical Synthesis 225 h. Electrochemical Synthesis 226
11. Properties of Complexes Containing Metal-Carbon a Bonds 227 a. Complexes of Group 3 Metals 227 b. Complexes of Group 4 Metals 229 c. Complexes of Group 5 Metals 232 d. Complexes of Group 6 Metals 232 e. Complexes of Group 7 Metals 234 f. Complexes of Group 8 Metals 238 g. Complexes of Group 9 Metals 242 h. Complexes of Group 10 Metals 244 i. Complexes of Group 11 Metals 249
12. Reactions of Complexes Containing Metal-Carbon a Bonds 253 a. The Breaking of the Metal-Carbon Bond ^ 253 b. Migration (Insertion) Reactions 255 c. Oxidative Addition Reactions 260 d. The o-n Rearrangement of Complexes Containing a Metal-Carbon Bonds 261
13. Activation of Hydrocarbons 262 References 269
Chapter 5. Carbene and Carbyne Complexes 1. Bonding 277 2. Structures of Carbene and Carbyne Complexes 281 3. IR Spectra 285 4. NMR Spectra 285 5. Photoelectron Spectra 287 6. Electronic Spectra 290 7. ESR and Magnetic Properties 291
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8. Methods of Preparation of Carbene Complexes 292 a. From Metal Carbonyls 292 b. Nucleophilic Addition to Isocyanide Ligands 292 c. Hydrogen Atom Abstraction from a Bonded Carbon Ligands 294 d. Alkylation of Complexes with Some M—Ca Bonds 295 e. Electrophilic Addition to Coordinated Ligands 295 f. Reactions of Complexes with Mixtures of Acetylenes and Alcohols 295 g. Synthesis from Ionic Complexes 295 h. Oxidative Addition Reactions 296 i. Reactions of Complexes with Neutral Carbene Precursors 297 j . Nucleophilic Addition to Carbyne Complexes 298 k. Oxidation Reactions 298 1. Addition to Carbonyl Ligands 298 m. Synthesis of /i-Methylene Complexes 299
9. Methods of Preparation of Carbyne Complexes 300 a. Removaf of Alkoxy, Alkylthio, and Amino Groups from the Carbene
Ligand 300 b. Hydrogen Elimination from the Carbene Ligand 300 c. Cleavage of C = C Bonds in Acetylenes and C s N Bonds in Cyanides 300 d. Reactions of Carbyne Complexes with Anionic Transition Metal
Complexes 301 e. Spontaneous Carbene Ligand Rearrangement 301 f. Reactions of Acyl Complexes with Dibromotriphenyl Phosphorus(V) 301 g. Oxygen Abstraction from Acyl Ligands 306 h. Protonation of Isocyanide Ligands 306 i. Miscellaneous Methods of Synthesis of Carbyne Complexes 306
10. Properties of Carbene and Carbyne Complexes 307 11. Reactions of Carbene Complexes 308
a. Nucleophilic Substitution Reactions 308 b. Rearrangement Reactions Caused by Addition 311 c. Hydrogen Substitution at a — C 312 d. Reduction of Carbene Complexes 312 e. Oxidation Reactions 313 f. Reactions with Electrophiles 314 g. Substitution Reactions of Noncarbene Ligands 314 h. Release of Carbene Ligands 315 i. Migration Reactions 317
12. Reaction of Carbyne Complexes 317 a. Reactions with Nucleophiles 317 b. Reactions Leading to Bridging Carbyne Complexes 318 c. Reactions of Carbyne Complexes with CO and COz 318 d. Removal of Carbyne Ligands 319 e. Exchange Reactions Involving Noncarbyne Ligands 320 f. Reactions with Acids 320 g. Miscellaneous Reactions 320
13. Reactions of Complexes Containing Methylene Bridges 320 14. Applications of Carbene and Carbyne Complexes 322 References 324
Contents xi
Chapter 6. Compounds Containing Two-Electron n-Ligands A. Olefin Complexes
1. Bonding and Structure 327 2. IR Spectra of Olefin Complexes 333 3. 'H NMR Spectra 335 4. 13C NMR Spectra 337 5. Photoelectron Spectra 339 6. Electronic Spectra 341 7. Stability of Olefin Complexes 343 8. Methods of Synthesis of Olefin Compounds 347
a. Olefin Addition to the Transition Metal Salts 347 b. Addition of Olefins to Coordination Compounds of the Transition Metals 347 c. Substitution of Coordinated Ligands with Olefins 347 d. Reduction in the Presence of Olefins 349 e. Preparation of Olefin Complexes from Hydrocarbon Ligands Coordinated
to the Metal 350 f. Exchange Reactions 350 g. Dehydration of Alcohols 351 h. Electrochemical Syntheses 351
9. Properties of Transition Metal Olefin Complexes 351 a. Group 4 Metal Complexes 352 b. Group 5 Metal Complexes 352 c. Group 6 Metal Complexes 353 d. Group 7 Metal Complexes 356 e. Group 8 Metal Complexes 358 f. Group 9 Metal Complexes 361 g. Group 10 Metal Complexes 368 h. Group 11 Metal Complexes 377
10. Complexes Containing Heteroolefins 379 11. Applications of rc-Olefin Complexes 381
a. Reactions of Olefin Complexes with Nucleophiles 381 b. Reactions of Olefin Complexes with Electrophiles 384 c. Amination of Olefins 386 d. Olefin Exchange Reactions 386 e. Substitution of Olefin Ligands 386 f. Transformation of Olefin Complexes into Vinyl Compounds 386 g. Hydrogen/Deuterium Exchange in Olefin Compounds 387 h. Photochemical Reactions 388
B. Acetylene Complexes 1. Bonding and Structure 389 2. IR Spectra 392 3. NMR Spectra 394 4. Methods of Preparation of Acetylene Complexes 396
a. Alkyne Addition to the Transition Metal Salts and Complexes 396 b. Ligand Substitution in Coordination Compounds 397
5. Properties of Acetylene Complexes 398 6. Reactions of Acetylene Complexes 404 7. Metallacyclization Reactions 409
xii Contents
8. Complexes Containing R —CsY and R - Y s C Ligands 412 C. Allene Complexes
1. Bonding and Structure 415 2. IR and NMR Spectra. Reactions of Allene Complexes 417
References 421
Chapter 7. Complexes Containing Three-Electron n-Ligands 1. The Metal-Allyl Bond 427 2. IR Spectra of AUyl Complexes 431 3. NMR Spectra 432 4. Electronic Spectra 439 5. Structural Properties 441 6. Photoelectron Spectra 441 7. Methods of Preparation of rc-AHyl Complexes 444
a. Reactions of Transition Metal Complexes with AUyl Compounds of Main Group Metals 444
b. Reactions of AUyl Halides with Transition Metal Complexes in the Presence of Reducing Agents 444
c. Oxidative Addition of AUyl Halides 445 d. Reactions of Olefins with Metal Complexes 445 e. Reactions of 1,3-Dienes with Metal Compounds 446 f. Rearrangements of a-Allyl Compounds to Tt-AUyl Compounds 447 g. Synthesis of Metal Complexes Containing Chelated AUyl Ligands 447 h. Miscellaneous Methods 448
8. Properties of 7t-AUyl Metal Compounds 450 a. Complexes of Group 4 Metals 450 b. Complexes of Group 5 Metals 451 c. Complexes of Group 6 Metals 451 d. Complexes of Group 7 Metals 453 e. Complexes of Group 8 Metals 454 f. Complexes of Group 9 Metals 458 g. Complexes of Group 10 Metals 459 h. Complexes of Group 3 Metals 460
9. Cyclopropenyl Complexes 461 10. Heteroallyl Complexes : 462 11. Reactions of AUyl Complexes 463
a. Thermal Decomposition 463 b. Interactions with Nucleophilic Reagents; Oxidative Hydrolysis 464 c. Electrophilic Attack on AUyl Groups 466 d. Formation of a-AUyl Complexes 466 e. Reduction 466 f. Reductive Elimination 467 g. Migration (Insertion) Reactions of Ligands 467
References 468
Chapter 8. Compounds Containing Four-Electron n-Ligands 1. The Bonding 471 2. Structure of Compounds with 4e Ligands 476
Contents xm
3. NMR Spectra 480 4. Photoelectron Spectra 485 5. IR Spectra ( 485 6. Methods of Preparation of 1,3-Diene Complexes 485
a. Reaction of Coordination Compounds with Dienes 485 b. Reactions Involving Nucleophilic Attack on Diene Complexes 488
7. Methods of Preparation of Cyclobutadiene Complexes 489 8. Methods of Preparation of Trimethylenemethane Complexes 496 9. Reactions of 1,3-Diene Complexes 498
10. Reactions of Cyclobutadiene Complexes 500 a. Thermal Decomposition 500 b. Ligand Substitution Reactions 500 c. Reactions Involving the Cyclobutadiene Ligand 501
Nucleophilic Attack 501 Electrophilic Attack 502
d. Oxidation Reactions 502 e. Reduction Reactions 503
11. Reactions of Trimethylenemethane Complexes 504 12. Properties of Diene Complexes 504 References 505
Chapter 9. Compounds Containing Five-Electron n-Ligands 1. The Metal-Cyclopentadienyl Bond 510 2. Structure of Cyclopentadienyl Complexes 518 3. NMR Spectra 520 4. IR Spectra 522 5. Magnetic Properties 524 6. EPR Spectra 525 7. Electronic Spectra 525 8. Photoelectron Spectra 527 9. Thermochemistry of Cyclopentadienyl Complexes 528
10. Mass Spectra 529 11. Methods of Preparation of Cyclopentadienyl Complexes 530
a. Reactions Utilizing Cyclopentadiene in the Presence of Bases or Cyclopentadienyl Compounds of the Main Group Elements 530
b. Syntheses Utilizing Fulvenes 531 c. Reactions of Transition Metal Compounds with Unsaturated
Hydrocarbons 532 d. Syntheses Utilizing Cyclopentadiene 533 e. Reactions of Dienes with Metal Vapors 533 f. Preparation of Triple-Decker Cyclopentadienyl Complexes 534 g. Preparation of Compounds Containing Bridging Cyclopentadienyl Ligands 536 h. Synthesis of Trinuclear M —P(0)(OR)2-Cyclopentadienyl Complexes 536 i. Electrochemical Synthesis 537^ j . Synthesis of Dienyl Complexes 537
12. Properties of Cyclopentadienyl Complexes 538 a. Group 4 Metal Complexes 538 b. Group 5 Metal Complexes 541
XIV Contents
c. Group 6 Metal Complexes 543 d. Group 7 Metal Complexes 545 e. Group 8 Metal Complexes 545 f. Group 9 Metal Complexes 548 g. Group 10 Metal Complexes 550 h. Group 11 Metal Complexes 551 i. Group 3 Metal Complexes Including Compounds of the Lanthanides and
the Actinides 551 13. Polynuclear and Cluster Cyclopentadienyl Complexes 554 14. Pentadienyl Complexes 554 15. Pyrrole Complexes 555 16. Multidecker Complexes 556 17. Reactions of Cyclopentadienyl Compounds 557
a. Oxidation of Metallocenes and Electron Transfer Reactions 557 b. Reduction of Cyclopentadienyl Complexes 558 c. Protonation 559 d. The M - c p Bond Rupture 559 e. Metallation Reactions 561 f. Aromatic Substitution Reactions 563 g. Preparation of Polymetallocenes 564 h. Ligand Substitution Reactions 564 i. Reactions with Substituents Containing Various Functional Groups 564 j . Activation of C — H Bonds 565 k. Photochemistry of Cyclopentadienyl Complexes 565
18. Application of Cyclopentadienyl Complexes 565 References 569
Chapter 10. Complexes Containing Six-Electron n-Ligands 1. The Bonding 575 2. Electronic Spectra of Arene Complexes 578 3. Magnetic Properties 578 4. IR Spectra 579 5. NMR Spectra 579 6. Photoelectron Spectra 580 7. ESR Spectra 582 8. Structure of Arene Complexes 583 9. Thermochemistry of Arene Complexes 584
10. Mass Spectra 585 11. Properties of Arene Compounds 586 12. Asymmetrie Arene Complexes 588 13. Triple Layer and Heteroarene Complexes 588 14. Methods of Preparation of Arene Complexes 590
a. Reactions of Transition Metal Compounds with Aluminum and Aluminum Chloride 590
b. Reactions of Salts of Metals with Grignard Compounds 590 c. Cyclotrimerization of Acetylenes 591 d. Dehydrogenation of 1,3-Cyclohexadiene 592 e. Substitution of Ligands 592
Contents xv
f. Reactions Involving Rearrangement of Ligands 593 g. Condensation of Metal Vapors with Ligands 594 h. Miscellaneous Reactions 594
15. Reactions of Arene Complexes 594 a. Redox Reactions 594 b. Electrophilic Substitution Reactions 596 c. Nucleophilic Substitution and Addition Reactions 596 d. Displacement of Ligands 598
16. Application of Arene Complexes 599 References 600
Chapter 11. Complexes Containing Seven- and Eight-Electron n-Ligands 1. Bonding, Structure, Spectroscopy, and Magnetic Properties 603 2. Properties of Cycloheptatrienyl and Cyclooctatetraene
Complexes 607 3. Methods of Preparation of Cycloheptatrienyl and Cyclooctatetraene
Complexes 609 4. Reactions of Cycloheptatrienyl and Cyclooctatetraene Complexes 611
a. Reactions with Nucleophiles 611 b. Oxidation and Reduction Reactions 613 c. Ligand Exchange Reactions in Complexes Containing CHT 614 d. The M-C„H„ Bond Breaking .' 614 e. Metallation Reactions 615
References 616
Chapter 12. Isocyanide Complexes 1. Bonding and Structure 617 2. Electronic Spectra 620 3. NMR Spectra 621 4. IR Spectra 622 5. ESR Spectra and Magnetic Properties 624 6. Ultraviolet and X-Ray Photoelectron Spectra 624 7. Properties of Isocyanide Complexes 624
a. Group 3 Metal Complexes 624 b. Group 4 Metal Complexes 625 c. Group 5 Metal Complexes 626 d. Group 6 Metal Complexes 626 e. Group 7 Metal Complexes 626 f. Group 8 Metal Complexes 627 g. Group 9 Metal Complexes 627 h. Group 10 Metal Complexes 628 i. Group 11 Metal Complexes 629
8. Methods of Synthesis of Isocyanide Complexes 629 a. Preparations Involving Metal Cyanides and Cyanide Metal Complexes.... 629 b. Reactions of Isocyanides with Transition Metal Compounds 631 c. Oxidation and Reduction Reactions 632
9. Reactions of Isocyanide Complexes 632 a. Cleavage of the M - C N R Bond 632
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xvi Contents
b. Oxidation-Reduction Reactions 633 c. Oxidative Addition Reactions 634 d. Nucleophilic Addition 634 e. Formation of Metal Carbyne Complexes 635 f. Insertion Reactions . 636 g. Dimerization of Isocyanides 639
10. Applications of Isocyanide Complexes 640 References 641
Chapter 13. Application of Organometallic Compounds in Homogeneous Catalysis 1. Basic Principles 647
a. Migration Reactions 652 b. Oxidative Coupling Reactions 654 c. Oxidative Addition Reactions 654
2. Hydrogenation 655 a. Olefin Hydrogenation 655 b. Hydrogenation of Aromatic Compounds 662 c. Asymmetrie Hydrogenation 662 d. Hydrogenation of the C = 0 , C = N, and C = N Bonds 667
3. Isomerization of Olefins 670 a. Migration of the Double Bond 670 b. Cis-Trans Isomerization 673
4. Oligomerization and Polymerization of Olefins and Acetylenes 674 a. Polymerization 674 b. Oligomerization 680
5. Carbonylation Reactions 690 a. Hydroformylation Reactions 690 b. Carbonylation Reactions 694 c. The Stability of Phosphine-Containing Catalysts for Hydroformylation . . . . 701
6. Hydrocyanation 702 7. Hydrosilation 703 8. Metathesis 704
a. Olefin Metathesis 704 b. Mechanism of the Metathesis Reaction 707 c. Metathesis of Functionalized Olefins 713 d. Metathesis of Alkynes 713
9. Disproportionation Reactions 713 10. Reduction of Carbon Monoxide; the Fischer-Tropsch Synthesis 714
a. Mechanism of the Fischer-Tropsch Reaction 716 11. Reactions of Carbon Dioxide 725 12. Water-Gas Shift Reaction 729 13. Amination and Amoxidation Reactions 731 14. Heterogenized Homogeneous Catalysts 732 References 736
Abbreviations 745
Index 749
