DeutschesFachbuch.de : Organometallics Von Christoph Elschenbroich

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Contents
Preface to the Third EditionV
Preface to the First EditionVII
Introduction
1 Milestones in Organometallic Chemistry 3
2 Organoelement Compounds: Classification and Electronegativity Considerations 11
3 Energy, Polarity, and Reactivity of the M-C Bond 15
3.1 Stability of Main-Group Organometallic Compounds 15
3.2 Lability of Main-Group Organometallic Compounds 17
Excursion 1: Where does our knowledge of M-C bond energies come from?19
Main-Croup Organometallics
4 Overview of Preparation Methods 27
5 Organometallic Chemistry of Alkali Metals (Group 1)33
5.1 Organolithium Compounds 33
Excursion 2: 6 Li and 7 Li NMR Spectroscopy of Organolithium Compounds 39
5.2 Organometallic Compounds of the Heavier Alkali Metals 50
Excursion 3: EPR Spectroscopy of Organoalkali-Metal Compounds 55
6 Organometallic Compounds of Groups 2 and 1259
6.1 Organometallic Compounds of the Alkaline-Earth Metals (Group 2)59
6.1.1 Organoberyllium Compounds 59
6.1.2 Organomagnesium Compounds 62
6.1.3 Organocalcium, -strontium, and -barium Compounds 70
6.2 Organometallic Compounds of Zn, Cd, Hg (Group 12)73
6.2.1 Organozinc Compounds 73
6.2.2 Organocadmium Compounds 77
6.2.3 Organomercury Compounds 78
Excursion 4: Organomercury Compounds in vivo 82
7 Organometallic Compounds of the Boron Group (Croup 13)87
7.1 Organoboron Compounds 87
7.1.1 Organoboranes 87
7.1.2 Organoboron-Transition-Metal Compounds 93
7.1.3 Boron Heterocycles 94
7.1.4 Polyhedral Boranes, Carbaboranes, and Heterocarbaboranes 99
Excursion 5: 11 B NMR Spectroscopy of Organoboron Compounds 108
7.2 Organoaluminum Compounds 110
7.2.1 OrganoaluminumIII Compounds 111
7.2.2 Subvalent Organoaluminum Compounds 123
7.3 Gallium, Indium, and Thallium Organyls 126
7.3.1 GaIII, InIII, and TlIII Organyls and their Lewis Base Adducts 126
7.3.2 GaIII, InIII, and TlIII Organyls 129
7.3.3 Thallium in Organic Synthesis 136
8 Organoelement Compounds of the Carbon Croup (Group 14)139
8.1 Organosilicon Compounds 142
8.1.1 Silicon Organyls of Coordination Number 4142
8.1.2 Organosilicon Compounds with Coordination Numbers 3, 2, and 1 and Their Subsequ...
8.2 Organogermanium Compounds 171
8.2.1 Germanium Organyls of Coordination Number 4171
8.2.2 Organogermanium Compounds with Coordination Numbers 3, 2, and 1 and Their Subse...
8.3 Organotin Compounds 179
Excursion 6: 119 Sn Mössbauer and 119 Sn NMR Spectroscopy 179
8.3.1 Organotin Compounds with Coordination Numbers 6, 5, and 4 and Their Subsequent ...
8.3.2 Organotin Compounds with Coordination Numbers 3, 2, and 1 and Their Subsequent ...
8.4 Organolead Compounds 198
8.4.1 PbIV Organyls 199
8.4.2 PbIII, PbII, and PbI Organyls 203
9 Organoelement Compounds of the Nitrogen Group (Group 15)211
9.1 EV Organyls (E = As, Sb, Bi)212
9.1.1 Pentaorganoelement Compounds R 5 E 212
9.1.2 Organoelement Derivatives RnEX 5 n 215
9.2 EIII Organyls (E = As, Sb, Bi)217
9.2.1 Trisorganoelement Compounds R 3 E 218
9.2.2 Organoelement Derivatives RnEX 3-n 221
9.3 Chains and Rings Containing E-E Single Bonds 224
9.4 E (P, As, Sb, Bi) as Partners in Multiple Bonds 229
9.4.1 E = C(pπ-pπ) Bonds 229
9.4.2 E ≡ C(pπ-pπ) Bonds 232
9.4.3 E = E(pπ-pπ) Bonds 235
9.4.3 E ≡ E((pπ-pπ)) Bonds 237
10 Organoelement Compounds of Selenium and Tellurium (Group 16)239
11 Organometallic Compounds of Copper, Silver, and Cold (Group 11)249
11.1 Copper and Silver Organyls 249
11.2 Gold Organyls 262
Organometallic Compounds of the Transition Metals
12 Introduction 275
12.1 The 18 Valence Electron (18 VE) Rule 276
Excursion 7: Can the VSEPR concept be applied to transition-metal complexes?282
12.2 Organometallic Catalysis: Some Fundamental Principles 284
13σ-Donor Ligands 291
13.1 Preparation of Transition-Metal-Alkyl and -Aryl Compounds 292
13.2 Selected Properties of Transition-Metal σ-Organyls 295
13.2.1 Thermodynamic Stability versus Kinetic Lability 295
13.2.2 Interactions of C-H σ Bonds with Transition Metals 299
13.2.3 Interaction of C-C σ Bonds with Transition Metals 308
13.2.4 Transition-Metal Perfluorocarbon σ Complexes 312
13.3 Transition-Metal Organyls In Vivo 315
14σ-Donor/π-Acceptor Ligands 329
14.1 Transition-Metal-Alkenyl, -Aryl, and -Alkynyl Complexes 329
14.2 Transition-Metal Carbene Complexes 333
14.3 Transition-Metal-Carbyne Complexes 350
14.4 Metal Carbonyls 356
14.4.1 Preparation, Structure, and Properties 357
14.4.2 Variants of CO Bridging 360
14.4.3 Bonding Properties and Experimental Evidence 363
14.4.4 Principal Reaction Types 372
14.4.5 Carbonyl Metalates and Carbonyl Metal Hydrides 375
14.4.6 Carbonyl Metal Halides 378
14.5 Thio-, Seleno-, and Tellurocarbonyl Metal Complexes 379
14.6 Isocyanide Complexes (Metal Isonitriles)381
Excursion 8: Photochemistry of Organometallic Compounds 383
15σ, π-Donor/π-Acceptor Ligands 395
15.1 Olefin Complexes 395
15.1.1 Homoalkene Complexes 395
15.1.2 Heteroalkene Complexes 413
15.1.3 Homo- and Heteroallene Complexes 415
15.2 Alkyne Complexes 424
15.2.1 Homoalkyne Complexes 425
15.2.2 Heteroalkyne Complexes 435
15.3 Allyl and Enyl Complexes 436
15.3.1 Allyl Complexes 436
15.3.2 Dienyl and Trienyl Complexes 445
Excursion 9: NMR Spectroscopy of Organometallic Compounds 451
15.4 Complexes of the Cyclic π-Perimeters CnHn 478
15.4.1 C 3 R 3+ as a Ligand 479
15.4.2 C 4 H 4 as a Ligand 480
15.4.3 C 5 H 5- as a Ligand 484
15.4.3.1 Binary Cyclopentadienyl-Metal Complexes 486
15.4.3.2 Cyclopentadienyl Metal Carbonyls 507
15.4.3.3 Cyclopentadienyl Metal Nitrosyls 511
15.4.3.4 Cyclopentadienyl Metal Hydrides 512
15.4.3.5 Cyclopentadienyl Metal Halides and Their Products 514
15.4.3.6 Special Applications of Metallocene Derivatives 518
15.4.4 C 6 H 6 as a Ligand 528
15.4.4.1 Bis(arene)metal Complexes 528
15.4.4.2 Arene Metal Carbonyls 539
15.4.4.3 Other Complexes of the Type (η6-Arene)MLn 543
15.4.4.4 Benzene Cyclopentadienyl Complexes 544
Excursion 10: Organometallic Chemistry of Fullerenes 546
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Author Index
A
Abel, E.W.
- 162: JCSD 1976, 2484
Abeles, R.H. 749
Ackermann, J. 745
Adams, R.D. 755, 756, 760
Adamson, A.W. 739
Ager, D. 745
Ahlrichs, R.
- 36: CPL 1986, 2, 172
Åkermark, B.
- 644: OM 1999, 18, 970
Akiba, K.
- 239: JACS 1999, 121, 10852
- 241: ACIE 1996, 35, 2638
- JACS 1999, 121, 10852
Albano, V.G.
- 605: JCSD 1973, 651
Albert, M.R. 740
Albracht, S.P.J.
- 322: NAT 1997, 385, 126
Albright, T.A
- 739, 751, 754
Alcock, N.W.
- 226: AICR 1972, 15, 1
Aldridge, S.
- 94: CC 2002, 856
- 94: JACS 2003, 125, 6356
Allegra, G.
- 553: RSR 1961, 1, (IIA) 362
- 558: JACS 1968, 90, 4455
Allen, F.H. 738
- 321: JCSP II, 1987, S 1
Allen, T.L.
- 136: JCSD 2000, 407
Allinger, N.L.
- 72: JACS 1995, 117, 7452
Almlöf, J. 742
Alper, H.G. 756
Alt, H.G. 760
- 392: ACIE 1984, 25, 729
- 706: JCSD 1999, 1703
Amatore, C. 758
- 643, 646: ACR 2000, 33, 314
Amma, E.L.
- 197: IC 1979, 18, 751
- 207: IC 1974, 13, 2429
Ammeter, J.H.
- 496: JACS 1974, 96, 7833
Anderson, G.K. 748
- 287: ACR 1984, 17, 67
Anderson, R.A.
- 617: JACS 1986, 108, 335
- 617: OM 2002, 21, 3100
- 619: JACS 1987, 109, 915
- 619: JACS 1987, 109, 941
- 625: OM 1988, 7, 1329
Andrews, L.
- 36: JCP 1967, 47, 4834
- 133: CC 1999, 2243
- 617: JACS 1999, 121, 12188
Andrews, M.A.
- 381: IC 1977, 16, 496
Angelici, R.J. 753
- 234: OM 1999, 18, 258
- 379: JACS 1968, 90, 3282;
- 379: JACS 1973, 95, 7516
- 380: IC 1987, 26, 452;
- 380: IC 1977, 16, 1173
- 380: JOM 1976, 117, C 75
- 561: OM 1987, 6, 1146
Angermund, K. 738
Antonova, A.B.
- 347: JOM 1977, 137, 55
Apeloig, Y. 746
- 79: AC I.E: 1999, 38, 1100
- 166: OM 1997, 16, 310
Arduengo III, A.J. 750
- 337: JACS 1991, 113, 361
- 337: JACS 1995, 117, 11027
- 616: JACS 1994, 116, 7927
Aresta, M.
- 419: CC 1975, 636
- 420: IC 1992, 31, 4286.
Armentrout, P.B.
- 23: ACR 1989, 22, 315
- 23: JACS 1988, 110, 411
- 23: JCP 1985, 83, 166
- 24: ACR 1995, 28, 403
- 269: JACS 1995, 117, 4071
- 741, 750
Arnett, E.M.
- 429: JACS 1964, 86, 4729
Ashby, E.C. 742
Ashe, III, A.J.
- 97: JACS 1979, 101, 7066
- 97: OM 1993, 12, 3225
- 128: ACIE 1995, 34, 1479
- 147: JACS 1970, 92, 1233
- 225: OM 1984, 3, 337
- 229: JACS 1971, 93, 3293
- 230: JOC 1981, 46, 881
- 565: ACIE 1987, 26, 229
- 566: OM 1995, 14, 2689
- 568: JACS 1977, 99, 8099
- 574: JACS 1996, 118, 2291
- 574: JACS 1975, 97, 6865;
- 576: ACIE 1993, 32, 1065
- 743, 747, 754, 755
Astruc, D.
- 544: TH 1983, 39, 4027
- 735, 739, 751, 753, 754
Atherton, N.M.
- 56: TFS 1966, 62, 1702
Atkins, R.W. 735
Atwood, J.D. 739
- 123: ACIE 1987, 26, 485
Aubke, F.
- 268: CCR 1994, 137, 483
- 269: JACS 1992, 114, 8972
Aulbach, M. 760
Auner, N. 746
Aylett, B.J. 745
- 735, 746
B
Bach, R.
Back, T.G. 747
Bäckvall, J.E. 759
- 639: JOC 1992, 57, 1588
- 661: JACS 1979, 101, 2411
- 663: JACS 1985, 107, 3676
Baerends, E.J.
- 72: POL 1990, 9, 1919
- 361: NJC 1991, 15, 815
- 386: JACS 1999, 121, 10356
Bahrmann, H. 758
Bailey, W.F. 742
- 29: JOM 1988, 352, 1
- 29: JOC 1998, 63, 9960
Baird, M.C.
- 507: OM 1990, 9, 2248
- 545: JOM 1972, 44, 383
Balch, A.L.
- 546: CHR 1998, 98, 2123
Baldwin, W. 753
Ball, G.E.
- 305: JACS 1998, 120, 9953
Bancroft, G.M.
- 180: AICR 1972, 15, 59
- 737, 738
Banerjee, R. 749
Banks, R.L.
- 682: JMC 1982, 15, 21
Barbier, P.
- 4: JCS 1899, 76, 323
Bard, A.J.
- 718: IC 1993, 32, 3528
Barron, A.R. 744
- 119: JACS 1995, 117, 6465
Barshik, C.M. 738
Bartell, L.S.
- 130: JCP 1964, 41, 717
Barton, D.H.R.
- 244: CC 1975, 539
Barton, T.J. 745
- 158: JOM 1972, 42, C 21
- 161: JOM 1979, 179, C 17
- 176: JACS 1973, 95, 3078
Basolo, F. 751
- 499: JACS 1984, 106, 5908
Basset, J.-M. 757
Bast, P.
Bau, R.
- 402: IC 1975, 14, 2653
- 589: IC 2004, 43, 555
- 604: ACIE: 1979, 18, 80
- 616: OM 1990, 9, 694
- 739, 751
Baudler, M.
- 227: ACIE 1985, 24, 991
Baxter, J.T. 742
Bazan, G.C. 755
- 712: JACS 2000, 122, 1830
Beachley Jr., O.T.
- 130: JACS 1986, 108, 4666
- 130: OM 1988, 7, 1051
Beattie, I.R.
- 61: AJC 1984, 37, 1601;
- 61: ICA 1992, 198-200, 309
- 299: IC 1979, 18, 2318
Beauchamp, A.L.
- 84: IC 1986, 25, 4870.
Beauchamp, J.L. 748
- 23: CHR 1990, 90, 629
- 331: CHR 1990, 90, 629
Bechgaard, K. 747
- 239: JACS 1981, 103, 2440
Beck, W.
- 741, 751
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