Inorganic Reactions and Methods, The Formation of Bonds to Transition and Inner-Transition Metals

by Zuckerman, J. J.; Hagen, A. P.

• ISBN13: 9780471192015
• ISBN10: 0471192015
• Edition: 1st
• Format: Hardcover
• Copyright: 1998-05-05
• Publisher: Wiley-VCH

Summary

Boasting numerous industrial applications, inorganic chemistry forms the basis for research into new materials and bioinorganic compounds such as calcium that act as biological catalysts. Now complete, this highly acclaimed series presents current knowledge in all areas of inorganic chemistry, including chemistry of the elements; organometallic, polymeric and solid-state materials; and compounds relevant to bioinorganic chemistry.

Author Biography

J. J. Zuckerman is the editor of Inorganic Reactions and Methods, Volume 14, The Formation of Bonds to Transition and Inner-Transition Metals, published by Wiley.

A. P. Hagen is the editor of Inorganic Reactions and Methods, Volume 14, The Formation of Bonds to Transition and Inner-Transition Metals, published by Wiley.

Table of Contents

How to use this Book	xix	(6)
Preface to the Series	xxv	(4)
Editorial Consultants to the Series	xxix	(2)
Contributors to Volume 14	xxxi
9. The Formation of the Bond to the Transition and Inner-Transition Metals	1	(112)
9.1. Introduction	2	(1)
9.2. The Formation of the Transition and Inner-Transition Metal to Transition and Inner-Transition Metal Bond	3	(104)
9.2.1. Introduction	3	(1)
9.2.2. In the Metal	3	(1)
9.2.2.1. From Oxides	3	(2)
9.2.2.2. From Sulfides	5	(1)
9.2.2.3. From Halides	6	(1)
9.2.2.3.1. Fluorides	6	(1)
9.2.2.3.2. Chlorides	6	(1)
9.2.2.4. From Other Compounds	7	(1)
9.2.2.4.1. Carbides	7	(1)
9.2.2.4.2. From Molten Salts (by Electrolysis)	7	(1)
9.2.2.5. Purification of Transition Metals	7	(1)
9.2.2.5.1. Preferential Oxidation or Reduction	7	(1)
9.2.2.5.2. Vacuum Melting, Distillation, and Zone Melting	8	(1)
9.2.2.5.3. Electrotransport	8	(1)
9.2.2.6. Chemical Separations of the Inner-Transition Metals	9	(1)
9.2.2.6.1. Chemical Separations by Oxidation-Reduction Processes	9	(1)
9.2.2.6.2. Ion Exchange Chromatography	9	(3)
9.2.2.6.3. Solvent Extraction	12	(1)
9.2.2.6.4. Extraction Chromatography	13	(1)
9.2.3. In Alloys and Clusters	13	(1)
9.2.3.1. From the Metals	13	(2)
9.2.3.2. From Compounds	15	(1)
9.2.3.3. Clusters	16	(1)
9.2.4. Between the Same Metals in Carbonyls and Their Derivatives	16	(1)
9.2.4.1. In Bi- and Polynuclear Metal Carbonyls	16	(1)
9.2.4.1.1. By Carbonylation and Reduction of Metal Oxides, Halides and Other Salts.	16	(2)
9.2.4.1.2. By Photolysis of Mononuclear Carbonyls.	18	(1)
9.2.4.1.3. By Thermolysis Reactions	19	(1)
9.2.4.2. In Bi-and Polynuclear Metal Carbonyl Anions and Carbonyl Hydrides	20	(1)
9.2.4.2.1. By Reactions of Monomeric Carbonyls	20	(1)
9.2.4.2.2. By Other Methods	21	(2)
9.2.4.3. In Substituted Carbonyls Containing Group VIB Ligands	23	(1)
9.2.4.4. In Substituted Carbonyls Containing Group VB Ligands	24	(3)
9.2.4.5. In Substituted Carbonyls Containing Two-Electron Group IVB Ligands	27	(2)
9.2.4.6. In Substituted Carbonyls Containing Three-Electron Group IVB Ligands	29	(2)
9.2.4.7. In Substituted Carbonyls Containing Four-Electron Group IVB Ligands	31	(2)
9.2.4.8. In Substituted Carbonyls Containing Five-Electron Group IVB Ligands	33	(2)
9.2.4.9. In Substituted Carbonyls Containing Six-Electron Group IVB Ligands	35	(2)
9.2.4.10. In Substituted Carbonyls Containing Other Group IVB Ligands	37	(1)
9.2.4.11. In Carbonyl Halides	38	(1)
9.2.4.12. In Cyanides and Isocyanides	38	(1)
9.2.4.13. In Nitrosyl Derivatives	39	(1)
9.2.5. Between Different Metals in Carbonyls and Their Derivatives	40	(1)
9.2.5.1. By Pyrolysis	40	(1)
9.2.5.2. By Photochemical Reactions	41	(1)
9.2.5.3. By Reactions of Carbonyls with Carbonyl Anions	41	(1)
9.2.5.4. By Reaction of a Metal Halide with a Metal Carbonyl Anion	42	(2)
9.2.5.5. By Reactions of Unsaturated or Weakly Stabilized Metal Complexes with Metal Nucleophiles	44	(2)
9.2.5.6. By Other Methods	46	(2)
9.2.6. Between First-Row Transition Metals (Excluding Chromium)	48	(1)
9.2.6.1. Formation of the Titanium-Titanium Bond	48	(1)
9.2.6.1.1. In Titanium Halides and Their Complexes	48	(1)
9.2.6.1.2. In Cyclopentadienyl and Related Titanium Complexes	49	(3)
9.2.6.2. Formation of the Vanadium-Vanadium Bond	52	(1)
9.2.6.3. Formation of the Manganese-Manganese Bond	53	(1)
9.2.6.4. Formation of the Iron-Iron Bond	53	(2)
9.2.6.5. Formation of the Cobalt-Cobalt Bond	55	(2)
9.2.6.6. Formation of the Nickel-Nickel Bond	57	(1)
9.2.6.7. Formation of the Copper-Copper Bond	58	(2)
9.2.7. Formation of the Chromium-Chromium Bond	60	(1)
9.2.7.1. From Aqueous Cr(II) Solutions	60	(1)
9.2.7.2. From Chromium Halides or Chromocene	61	(1)
9.2.7.3. From Substitution Reactions of Cr(2)(O(2)CCH(3))(4)	62	(2)
9.2.7.4. By Other Methods	64	(1)
9.2.8. Formation of Heavy Transition Metal Group V Metal-Metal Bonds	65	(1)
9.2.8.1. Synthesis of Hexanuclear Niobium and Tantalum Clusters	65	(1)
9.2.8.2. In Niobium and Tantalum Halides Without Hexanuclear Cluster Units	66	(1)
9.2.8.3. In Discrete Niobium and Tantalum Dimeric and Trimeric Complexes	67	(2)
9.2.9. Formation of Heavy Transition Metal Group VI Metal-Metal Bonds	69	(1)
9.2.9.1. Group VI Quadruple Bonds	69	(1)
9.2.9.1.1. Molybdenum(II) Dimer Synthesis	69	(2)
9.2.9.1.2. Tungsten(II) Dimer Synthesis	71	(1)
9.2.9.1.3. Mixed-Metal Group VI Dimers Containing MM(4+) Units	71	(1)
9.2.9.2. Unbridged Group VI M(2)X(6) Triple Bonds	71	(2)
9.2.9.3. Triply Bridged [M(2)X(9)](3-) Dimers	73	(1)
9.2.9.4. Group VI Metal-Metal Double Bonds	74	(2)
9.2.9.5. Dimers Containing Group VI Single Bonds	76	(1)
9.2.9.5.1. Molybdenum(V) Dimer Syntheses	76	(2)
9.2.9.5.2. Tungsten(V) Dimer Syntheses	78	(1)
9.2.9.6. Group VI Trimers with Metal-Metal Bonds	79	(1)
9.2.9.6.1. Molybdenum Trimer Syntheses	79	(1)
9.2.9.6.2. Tungsten Trimer Synthesis	80	(1)
9.2.9.7. Group VI Tetramers and Pentamers	81	(2)
9.2.9.8. Syntheses of Hexanuclear Molybdenum and Tungsten Clusters	83	(2)
9.2.10. Formation of Heavy Transition Metal Group VII Metal-Metal Bonds	85	(1)
9.2.10.1. Synthesis of Dimeric Technetium and Rhenium Compounds	85	(1)
9.2.10.1.1. Rhenium(III) Dimer Syntheses	85	(2)
9.2.10.1.2. Syntheses of Rhenium Dimers Without the Re(6+)(2) Unit	87	(2)
9.2.10.1.3. Syntheses of Technetium Dimers	89	(1)
9.2.10.2. Trimeric Rhenium Compounds	89	(2)
9.2.10.3. Rhenium Phosphides	91	(1)
9.2.11. Formation of Bonds Among Other Second- and Third-Row Group VIII Metals in the Absence of Acid Ligands	91	(1)
9.2.11.1. Conproportionation Reactions	92	(1)
9.2.11.2. Bridging Phosphines	93	(1)
9.2.11.2.1. Direct Reactions Without Oxidation-Reduction	93	(1)
9.2.11.2.2. Assisted Oxidative Addition of One Metal-Halogen Bond to a Second Metal	94	(1)
9.2.11.2.3. Binuclear Reductive Elimination	95	(1)
9.2.11.2.4. Formation of Triangular Arrays	95	(1)
9.2.11.2.5. Formation of Nearly Linear Trinuclear Arrays	96	(1)
9.2.11.3. Oxidative Addition	97	(1)
9.2.11.3.1. Oxidative Addition to Bridged Binuclear Compounds	97	(1)
9.2.11.3.2. Oxidative Addition to Mononuclear Compounds	97	(1)
9.2.11.4. The Disproportionation to Rh(I) and Rh(III)	98	(1)
9.2.11.5. Reductive Procedures	98	(1)
9.2.11.6. Miscellaneous Reactions	99	(1)
9.2.12. In Transition and Inner Transition Metal Complexes with Chains of Metal Atoms	99	(2)
9.2.12.1. Compounds Containing Nickel, Palladium, and Platinum Chains	101	(1)
9.2.12.1.1. Tetracyanoplatinates	101	(1)
9.2.12.1.2. Bis(oxalato)platinates	102	(1)
9.2.12.1.3. Triplatinum Tetraoxides	103	(1)
9.2.12.1.4. Halogen-Oxidized Complexes Containing XXX-Delocalized Ligands	103	(1)
9.2.12.2. Compounds Containing Rhodium and Iridium Chains	104	(1)
9.2.12.2.1. Halotricarbonyliridium(I)	104	(1)
9.2.12.2.2. Dihalodicarbonyliridates	105	(1)
9.2.12.3. Compounds Containing Mercury Chains	105	(2)
9.3. The Formation of the Transition Metal-Group 0 Element Bond	107	(6)
9.3.1. Introduction	107	(1)
9.3.2. Methods of Bond Formation and Characterization	108	(1)
9.3.2.1. Matrix Isolation	108	(2)
9.3.2.2. Liquified and Supercritical Noble Gases	110	(2)
9.3.2.3. Gas Phase Methods	112	(1)
10. Oxidative Addition and Reductive Elimination Reactions	113	(206)
10.1. Introduction	114	(1)
10.2. Oxidative Additions and Reductive Eliminations for Compounds of the Typical Elements	115	(78)
10.2.1. Introduction	115	(1)
10.2.2. Reactions at a Group IA Metal Center	115	(1)
10.2.2.1. Reactions of Organic Halides	116	(1)
10.2.2.2. Elemental Reactions	117	(1)
10.2.2.2.1. With Group VIIB Elements	117	(1)
10.2.2.2.2. With Group VIB Elements	117	(1)
(i) Oxygen	117	(2)
(ii) Sulfur, Selenium, and Tellurium	119	(1)
10.2.2.3. Reactions to Form Compounds Containing Zintl Anions	120	(1)
10.2.2.3.1. From Fusion of the Elements	121	(1)
(i) In Tantalum or Niobium Ampoules	121	(1)
(ii) In Boron Nitride Crucibles	121	(1)
(iii) In Quartz Reaction Vessels	121	(1)
(iv) In an Alumina Crucible	122	(1)
(v) From Fusion Followed by Extraction	122	(1)
10.2.2.3.2. From Molecular Precursors	122	(1)
10.2.2.4. Reactions to Form Alkalides	123	(1)
10.2.2.5. Reactions to Form Electrides	124	(1)
10.2.2.6. Reactions to Form Polylithiated Compounds	125	(1)
10.2.2.6.1. In Condensed Phases	125	(1)
(i) From Alkynes	125	(1)
(ii) From Halocarbons	126	(1)
(iii) From Metal Alkyls	127	(1)
10.2.2.6.2. By Pyrolysis	127	(1)
10.2.2.6.3. In The Gas Phase	128	(1)
(i) With Halocarbons: Perhalocarbons	129	(1)
(ii) With Halocarbons: Mono-and Dihalocarbons	129	(2)
(iii) From the Elements	131	(1)
(iv) From Alkenes	131	(1)
(v) From Metal Alkyls	131	(1)
10.2.3. Reactions at a Group IIA Metal Center (Excluding Ra)	131	(1)
10.2.3.1. Reaction of Halogens and Hydrogen Halacids	132	(1)
10.2.3.1.1. Reaction of Halogens	132	(1)
10.2.3.1.2. Reaction of Hydrogen Halacids	133	(1)
10.2.3.2. Reaction of Organic Halides	134	(1)
10.2.3.2.1. Grignard Reaction	134	(1)
10.2.3.2.2. Reaction of Organic Halides with Beryllium, Calcium, Srtrontium, and Barium	135	(1)
10.2.3.2.3. Structural Investigations of Organometallic Compounds	136	(1)
10.2.3.2.4. Oxidative Additions to Metal Atoms and Slurries	137	(1)
10.2.3.3. Reaction of Unsaturated Organic Molecules	138	(1)
10.2.3.3.1. Reactions with Magnesium	138	(1)
10.2.3.3.2. Reactions with Calcium, Strontium, and Barium	139	(1)
10.2.3.4. Reactions of Dioxygen-and Oxygen-Containing Compounds	140	(1)
10.2.3.4.1. Reactions of Dioxygen	140	(1)
10.2.3.4.2. Reactions of Oxygen-Containing Compounds	140	(1)
10.2.3.5. Reactions of Other Addenda, Excluding Metal-Metal Interactions and Alloys	141	(1)
10.2.4. Reactions at a Group IIIB Element Center	141	(2)
10.2.4.1. Reactions of Halogens and Hydrogen Halacids	143	(3)
10.2.4.2. Reactions of Organic Halides	146	(1)
10.2.4.2.1. Reactions with Compounds	146	(1)
10.2.4.2.2. Oxidative Addition to Metal Atoms and Slurries	147	(1)
10.2.4.3. Reactions of Dioxygen and Group VIB-Containing Compounds	148	(2)
10.2.4.4. Reactions of Hydrogen and Organic Addenda	150	(2)
10.2.4.5. Reactions of Metal Carbonyls and Other Transition Metal Compounds	152	(1)
10.2.5. Oxidative Addition and Reductive Elimination Reactions at a Group IVB Metal Center	153	(1)
10.2.5.1. Introduction	153	(1)
10.2.5.2. Reactions at Silicon(II) Centers	154	(2)
10.2.5.2.1. Insertions	156	(1)
(i) Into Elemental Bonds (O(2),S(8))	156	(1)
(ii) Into C=E Bonds (E=O,S,N)	157	(2)
(iii) Into E-H Bonds (E=O,S)	159	(1)
(iv) Into N-C (Aryl) Bonds	160	(1)
(v) Into B-N Triple Bonds	160	(1)
(vi) Into Si-H and C-H Bonds	160	(1)
10.2.5.2.2. Addition Reactions	161	(1)
(i) With Dienes	161	(1)
(ii) With Olefins	162	(1)
(iii) With Alkynes	162	(1)
(iv) With Arenes	162	(1)
(v) With Transition Metals	163	(2)
10.2.5.2.3. Other Reactions	165	(1)
(i) With Pyridyl Derivatives	165	(1)
(ii) With Azides	165	(1)
(iii) With Boranes	166	(1)
10.2.5.3. Reactions at Germanium(II) Centers	166	(2)
10.2.5.3.1. Insertions	168	(1)
10.2.5.3.2. Additions	169	(1)
(i) With Dienes	169	(1)
(ii) With Alkynes	169	(1)
(iii) With Transition Metals	170	(2)
(iv) With Carbenes	172	(1)
10.2.5.4. Reactions at Tin(II) Centers	172	(2)
10.2.5.4.1. Salt Elimination	174	(1)
10.2.5.4.2. Substitutions	174	(1)
10.2.5.4.3. With Molecular Oxygen	175	(1)
10.2.5.4.4. With Unsaturated Reagents	175	(1)
(i) Carbonyls and Ketenes	175	(1)
(ii) Transition Metal Complexes	176	(1)
10.2.5.5. Reactions at Lead(II) Centers	176	(1)
10.2.5.5.1. Salt Elimination	177	(1)
10.2.5.5.2. Insertions	177	(1)
10.2.5.6. Oxidative Addition of Organic Halides to Metal Atoms and Slurries	178	(1)
10.2.6. Reactions at a Group VB Element Center	179	(1)
10.2.6.1. Introduction	179	(1)
10.2.6.2. Oxidative Reactions Involving the Formation of Group VB Multiply Bonded Species	180	(1)
10.2.6.2.1. Introduction	180	(1)
10.2.6.2.2. Terminal Phosphinidenes	180	(1)
(i) Through Salt Eliminations	180	(1)
(ii) Through Phosphine Elimination	181	(1)
(iii) Through Oxidative Addition	182	(1)
10.2.6.3. Reductive Elimination Reactions	183	(1)
10.2.6.3.1. In the Arylation of Inorganic and Organic Substrates with Aryl Bismuth(V) Reagents	184	(1)
10.2.6.3.2. In the Oxidation of Organic Substrates	185	(1)
(i) With Aryl Bismuth Reagents	185	(1)
(ii) With Bismuth Ylides	185	(1)
10.2.7. Reactions at a Group VIB Element Center	186	(1)
10.2.7.1. Reactions of Halogens at an Oxygen Center	186	(1)
10.2.7.2. Reactions of Halogens at a Sulfur, Selenium, and Tellurium Center	187	(1)
10.2.7.3. Reactions of Other Addenda at an Oxygen Center	187	(1)
10.2.7.4. Reactions of Other Addenda at a Sulfur Center	188	(3)
10.2.7.5. Oxidative Additions to Metal Atoms and Slurries	191	(2)
10.3. Oxidative Additions and Reductive Eliminations to Compounds of the Transition Elements	193	(126)
10.3.1. Introduction	193	(1)
10.3.2. Reactions at a Group IIIA or IVA Metal Center	193	(1)
10.3.2.1. Reactions of Halogen-Containing Compounds	193	(6)
10.3.2.2. Reactions of Other Addenda	199	(5)
10.3.3. Reactions at a Group VA Metal Center	204	(1)
10.3.3.1. Reactions of Halogens, Halacids, and Other Halogen-Containing Compounds	204	(4)
10.3.3.2. Reactions of Other Addenda	208	(7)
10.3.4. Reactions at a Group VIA Metal Center	215	(1)
10.3.4.1. Reactions of Halogens	215	(3)
10.3.4.2. Reactions of Halogen Compounds of the Group IVB Elements	218	(3)
10.3.4.3. Reactions of Other Halogen-Containing Compounds	221	(1)
10.3.4.4. Reactions Forming Bonds to Hydrogen from Group VIB Hydrogen Addenda	222	(1)
10.3.4.5. Reactions of Other Addenda	223	(4)
10.3.5. Reactions at a Group VIIA Metal Center	227	(1)
10.3.5.1. Reactions of Halogen-Containing Compounds	227	(2)
10.3.5.2. Reactions Involving Hydrogen	229	(1)
10.3.5.3. Reactions Involving C-H and C-C Bonds	230	(2)
10.3.5.4. Reactions with Other Addenda	232	(1)
10.3.6. Reactions at a Group VIII Metal Center (The Fe, Ru and Os Triad)	233	(1)
10.3.6.1. Introduction	233	(1)
10.3.6.2. Reactions with Hydrogen	233	(2)
10.3.6.3. Reactions of C-H Bonds	235	(1)
10.3.6.3.1. With Organoiron Centers	235	(1)
10.3.6.3.2. With Organoruthenium Centers	236	(2)
10.3.6.3.3. With Organoosmium Centers	238	(2)
10.3.6.4. Reactions of O-H and Other Element-Hydrogen Bonds	240	(4)
10.3.6.5. Reactions of Halogen-Containing Compounds	244	(2)
10.3.6.6. Formation of Metal-Metal Bonds	246	(1)
10.3.6.7. Reaction of Other Addenda	246	(3)
10.3.7. Oxidative Addition and Reductive Elimination Reactions of Group VIII: Cobalt, Rhodium, and Iridium	249	(1)
10.3.7.1. Dihydrogen	250	(2)
10.3.7.2. Group VIII	252	(1)
10.3.7.2.1. Carbon-Hydrogen Bond Activation	252	(4)
10.3.7.2.2. Silanes and Other Group IVB Compounds	256	(1)
10.3.7.3. Reactions of Halacids and Halogens	257	(2)
10.3.7.4. Reactions of Other Halides	259	(3)
10.3.7.5. Oxidative Addition of Other Molecules	262	(2)
10.3.7.6. Reductive Elimination on Cobalt, Rhodium, and Iridium	264	(2)
10.3.8. Reactions at a Group VIII Metal Center: The Ni, Pd, Pt Triad	266	(1)
10.3.8.1. Reactions of Dihydrogen	266	(3)
10.3.8.2. Reactions of Hydrogen-Silicon Bonds	269	(1)
10.3.8.3. Reactions of Hydrogen-Germanium and Hydrogen-Tin Bonds	270	(2)
10.3.8.4. Reactions Involving Carbon-Hydrogen Bonds	272	(3)
10.3.8.5. Reactions of Carbon-Halogen Bonds	275	(4)
10.3.8.6. Reactions of Halogens and Hydrogen Halides	279	(5)
10.3.8.7. Formation of Metal-Metal Bonds	284	(4)
10.3.8.8. Cleavage and Formation of Carbon-Carbon Bonds	288	(6)
10.3.8.9. Reactions of Tin-Carbon and Lead-Carbon Bonds	294	(1)
10.3.8.10. Reactions of Carbon-Oxygen and Carbon-Nitrogen Bonds	295	(3)
10.3.8.11. Reactions of Oxygen-Hydrogen and Nitrogen-Hydrogen Bonds	298	(1)
10.3.8.12. Reactions with Other Addenda	298	(1)
10.3.9. Internal Oxidative-Addition Reactions (Cyclometallation)	299	(14)
10.3.10. Oxidative Addition to Metal Atoms and Slurries	313	(6)
11. Insertion Reactions and Their Reverse	319	(176)
11.1. Introduction	320	(1)
11.2. Insertion Reactions Into Element-Hydrogen Bonds	321	(30)
11.2.1. Introduction	321	(1)
11.2.1.1. Mechanism	322	(1)
11.2.1.2. Thermodynamics	323	(1)
11.2.2. Insertion Reactions of Olefins	323	(1)
11.2.2.1. Groups IA, IIA, and IIB	324	(1)
11.2.2.2. Group IIIB	324	(2)
11.2.2.3. Group IVB	326	(2)
11.2.2.4. Group VB	328	(2)
11.2.2.5. Group VIB and VIIB	330	(1)
11.2.2.6. Transition Metals	330	(5)
11.2.3. Insertion Reactions of Acetylenes	335	(1)
11.2.3.1. Main Group Hydrides	335	(2)
11.2.3.2. Transition Metal Hydride Complexes	337	(4)
11.2.4. Insertion Reactions of Carbon Dioxide and Carbon Disulfide	341	(2)
11.2.5. Insertion Reactions of O(2)	343	(1)
11.2.6. Insertion Reactions of Nitriles, Thiocyanates, Carbodiimides and Other Nitrogen-Containing Compounds	344	(3)
11.2.7. Other 1,2-Insertion Reactions	347	(1)
11.2.8. 1,1-Insertions of Carbon Monoxide and Isonitriles	348	(3)
11.3. Insertion Reactions into Element-Carbon Bonds	351	(76)
11.3.1. Introduction	351	(4)
11.3.2. 1,1 Insertion Reactions	355	(1)
11.3.2.1. Insertions of Carbon Monoxide	355	(1)
11.3.2.1.1. Mechanistic Studies and Stereochemistry of Carbon Monoxide Insertion Reactions.	356	(5)
11.3.2.1.2. Insertions of Carbon Monoxide in Complexes of Group IB Metals.	361	(1)
11.3.2.1.3. Insertions of Carbon Monoxide in Complexes of Group VIII Metals.	362	(1)
(i) Nickel, Palladium, and Platinum	362	(7)
(ii) Cobalt, Rhodium, and Iridium	369	(4)
(iii) Iron, Ruthenium, and Osmium	373	(3)
11.3.2.1.4. Insertion Reactions of Carbon Monoxide in Complexes of Group VIIA Metals (Mn, Tc, Re)	376	(4)
11.3.2.1.5. Insertion Reactions of Carbon Monoxide in Complexes of Group VIA Metals (Cr, Mo, W)	380	(2)
11.3.2.1.6. Insertions of Carbon Monoxide in Complexes of Groups VA (V, Nb, Ta) and IVA (Ti, Zr, Hf)	382	(1)
(i) Vanadium, Niobium, and Tantalum	382	(2)
(ii) Titanium, Zirconium, Hafnium	384	(3)
11.3.2.1.7. Insertions of Carbon Monoxide in Inner-Transition Metal Complexes	387	(2)
11.3.2.1.8. Carbon Monoxide Insertions in Metal-Hydrogen Bonds	389	(2)
11.3.2.2. Insertions of Isocyanides in Metal-Carbon XXX-bonds	391	(3)
11.3.2.3. Insertions of Sulfur Dioxide into Metal-Carbon Bonds	394	(3)
11.3.3. 1,2-and Higher Insertion Reactions	397	(2)
11.3.3.1. Insertion Reactions of Olefins	399	(9)
11.3.3.2. Insertion Reactions of Acetylenes	408	(7)
11.3.3.3. Insertion Reactions of Oxygen	415	(2)
11.3.3.4. Insertion Reactions of Carbon Dioxide, Sulfur Dioxide, and Sulfur Trioxide	417	(5)
11.3.3.5. Insertion Reactions of Nitric Oxide	422	(2)
11.3.3.6. Insertion Reactions of Dienes, Aldehydes, Ketones, and Isonitriles	424	(3)
11.4. Insertion Reactions into Element-Nitrogen and Heavier Group VB Bonds	427	(28)
11.4.1. Introduction	427	(6)
11.4.2. Reactions of an Amide with a 1,2-Dipole (Vicinal, or 1,2-Addition)	433	(1)
11.4.2.1. Insertion Reactions of an Alkene or Alkyne	433	(1)
11.4.2.2. Insertion Reactions of an Isocyanate, Isothiocyanate, Carbodiimide, Ketene, Diketene, or Ketenimine	434	(5)
11.4.2.3. Insertion Reactions of CO(2), CS(2), COS, CSe(2), SO(2), SeO(2), SO(3), PhNSO, S(4)N(4), or a P=N Bond	439	(5)
11.4.2.4. Insertion Reactions of an Aldehyde or Ketone, or of a Related Compound Having an Isolated ]C=O, ]C=S, -N=O, or -N(O)=O Bond	444	(3)
11.4.2.5. Insertion Reactions of a Nitrile	447	(1)
11.4.3. Geminal (or 1,1-) Addition of an Amide	448	(1)
11.4.3.1. Insertion Reactions of an Isonitrile	448	(1)
11.4.3.2. Insertion Reactions of Carbon Monoxide or a Metal Carbonyl (the Latter are 1,2-Additions)	449	(1)
11.4.4. Reactions of Amides with 1, 3-1, 4-, or 1, 5-Dipoles by Ring-Opening	450	(2)
11.4.5. Insertion Reactions into Element-Nitrogen Bonds of Compounds Other than Amides, and into Some Element-Phosphorus or-Arsenic Bonds	452	(3)
11.5. Insertion Reactions into Element-Oxygen and Heavier Group VIB Element Bonds	455	(14)
11.5.1. Introduction	455	(2)
11.5.2. Insertion Reactions of Carbon Dioxide, Carbon Disulfide, and Carbon Monoxide	457	(2)
11.5.3. Insertion Reactions of Isocyanates, Isothiocyanates, and Carbodiimides	459	(4)
11.5.4. Insertion Reactions of Aldehydes and Ketones	463	(1)
11.5.5. Insertion Reactions of Sulfur Dioxide, Sulfur Trioxide, Sulfodiimides, and Sulfinylamines	464	(1)
11.5.6. Insertion Reactions of Ketenes, Alkenes, and Alkynes	465	(4)
11.6. Insertion Reactions into Element-Halogen Bonds	469	(14)
11.6.1. Introduction	469	(1)
11.6.2. Insertions of Acetylenes and Olefins	469	(4)
11.6.3. Insertions of Allenes and Dienes	473	(1)
11.6.4. Insertion of Aldehydes, Ketones and Ketenes	474	(2)
11.6.5. Insertion of Sulfur and Selenium Trioxide	476	(1)
11.6.6. Insertions of Thiocyanates, Cyanates, Nitriles, Isonitriles, Imides	476	(1)
11.6.7. Ring-Opening Insertions	477	(1)
11.6.8. Carbene and Carbene Analog Insertions	478	(1)
11.6.9. Miscellaneous Insertions	479	(4)
11.7. Insertion Reactions into Metal-Metal Bonds	483	(12)
11.7.1. Introduction	483	(1)
11.7.2. Insertion Reactions of Acetylenes and Olefins	483	(2)
11.7.3. Insertion Reactions of Low-Valent Group IVB Halides	485	(3)
11.7.4. Insertion Reactions of Carbon Disulfide and Sulfur Dioxide	488	(2)
11.7.5. Other Insertion Reactions	490	(5)
Abbreviations	495	(8)
Author Index	503	(34)
Compound Index	537	(136)
Subject Index	673