Synthetic Coordination Chemistry: Principles and Practice

by Davies, J. A.; Hockensmith, C. M.; Kukushkin, V. Yu; Kukushkin, Yu N.

• ISBN13: 9789810220846
• ISBN10: 9810220847
• Format: Hardcover
• Copyright: 1997-05-01
• Publisher: World Scientific Pub Co Inc

Table of Contents

Acknowledgments	vii	(2)
Preface	ix	(2)
List of abbreviations	xi
Chapter 1. SYNTHESIS OF COORDINATION COMPOUNDS: THEORETICAL CONSIDERATIONS	1	(34)
1.1 Labile and inert coordination compounds	1	(2)
1.2 Synthesis of mixed-ligand complexes by co-proportionation	3	(1)
1.3 The chelate effect	4	(2)
1.4 The trans-effect	6	(4)
1.5 The cis-effect	10	(1)
1.6 Geometric isomerization of square-planar platinum(II) and palladium(II) complexes	11	(2)
1.7 The effective atomic number concept	13	(1)
1.8 The 16-/18-election rule	13	(1)
1.9 The hard-soft acid-base (HSAB) principle	13	(1)
1.10 Factors affecting the acid/base properties of coordination compounds	14	(6)
1.11 Ligand effects on redox potentials of coordination compounds	20	(6)
1.12 Reactivity of coordinated ligands	26	(5)
References	31	(4)
Chapter 2. THE SOLUBILITY OF COORDINATION COMPOUNDS: RELATIONSHIP TO COMPOSITION AND STRUCTURE	35	(23)
2.1 Hydrophilic and lipophilic coordinated ligands	36	(3)
2.2 Solubility of ionic complexes: counterion effects	39	(10)
2.3 Changes in solubility through modification of cationic counterions	49	(3)
2.4 Solubility of complexes in mixed solvents	52	(2)
References	54	(4)
Chapter 3. GENERATION OF SOLVENTO-COMPLEXES	58	(37)
3.1 Halide abstraction reactions	62	(7)
3.2 Solvento-complexes from redox transformations of coordination compounds	69	(7)
3.2.1 Redox transformations of N-donor ligands	69	(4)
3.2.2 Redox transformations with other classes of ligands	73	(1)
3.2.3 Oxidation or reduction of central atoms	74	(2)
3.3 Formation of solvento-complexes through reactins of coordinated ligands (non-redox)	76	(2)
3.4 Dehydration reactions of aqua-complexes and formation of solvento-complexes	78	(1)
3.5 Decarbonylation reactions and removal of other supporting ligands (olefins, acetylenes, arenes, dinitrogen)	79	(1)
3.6 Application of solvento-complexes in the synthesis of bridged hetero- and homopolynuclear complexes	80	(1)
3.7 Complexes containing coordinated halocarbons	81	(5)
References	86	(9)
Chapter 4. HOMOLEPTIC SOLVENTO-COMPLEXES: STARTING MATERIALS FOR PREPARATIVE COORDINATION CHEMISTRY	95	(62)
4.1 Introduction	95	(2)
4.2 Synthesis of solvento-complexes by metal oxidation in non-aqueous solvents	97	(2)
4.3 Synthesis of solvento-complexes by dissolution of salts in non-aqueous solvents	99	(2)
4.4 Synthesis of solvento-complexes by dehydration of aqua-complexes and hydrated salts	101	(2)
4.5 Synthesis of solvento-complexes by substitution of ligated solvent molecules	103	(1)
4.6 Synthesis of solvento-complexes by halide abstraction from salts and complexes	104	(38)
References	142	(15)
Chapter 5. SYNTHESIS VIA ION EXCHANGE IN NON-AQUEOUS SOLVENTS	157	(26)
5.1 Ligand substitution by ion exchange in non-aqueous solvents	157	(8)
5.2 Synthesis of complexes containing classically "noncoordinating" anions as ligands	165	(2)
5.3 Formation of chelate complexes by ion exchange in non-aqueous solvents	167	(2)
5.4 Synthesis of complexes containing metal-metal bonds between transition metals	169	(3)
5.5 Synthesis of complexes containing transition metal-main group metal/metalloid bonds	172	(3)
5.6 Replacement of counterions in ionic complexes	175	(2)
References	177	(6)
Chapter 6. SYNTHESIS OF BRIDGED COMPLEXES AND RING-CLOSURES	183	(12)
6.1 Synthesis of bridged complexes	183	(5)
6.2 Ring-closure reactions	188	(5)
References	193	(2)
Chapter 7. THE ELECTROSYNTHESIS OF COORDINATION COMPOUNDS	195	(27)
7.1 Electrochemical oxidation and reduction of complexes using inert electrodes	195	(5)
7.2 Electrochemically induced reactions	200	(4)
7.3 Electrosynthesis using a sacrificial anode	204	(8)
7.3.1 Preparation of anhydrous salts, metal halide complexes and solvento-complexes	204	(1)
7.3.2 Electrosynthesis of complexes containing weakly acidic anions	205	(4)
7.3.3 Electrosynthesis of organometallic compounds	209	(1)
7.3.4 Electrochemical reactions involving oxidative addition	210	(2)
7.4 Electrosynthesis at a sacrificial cathode	212	(1)
7.5 Practical considerations in synthetic electrochemistry	213	(3)
References	216	(6)
Chapter 8. NON-TRADITIONAL OXIDANTS IN PREPARATIVE COORDINATION CHEMISTRY	222	(70)
8.1 Nitrosonium, thionitrosonium and nitronium salts	222	(8)
8.2 Aryldiazonium salts	230	(3)
8.3 Triphenylcarbenium, tropylium, and other carbenium salts	233	(6)
8.4 Protic acids	239	(2)
8.5 Silver, mercury and other metal salts	241	(5)
8.6 Non-metal halides	246	(14)
8.6.1 Phosphorus halides	246	(6)
8.6.2 SOCl2 and SO2Cl2 as oxidants	252	(5)
8.6.3 Iodobenzene dichloride	257	(1)
8.6.4 Other non-metal halides	258	(2)
8.7 Aminoxides and other oxygen donors	260	(10)
8.8 Other selected oxidants	270	(3)
8.9 "Modification" of Water-soluble oxidants	273	(3)
References	276	(16)
Chapter 9. REDUCTANTS IN PREPARATIVE COORDINATION CHEMISTRY	292	(47)
9.1 Reduction by metals and amalgams	292	(4)
9.2 Reduction by organic radical-anions and anions	296	(5)
9.3 Carbon monoxide and other carbon-containing reductants	301	(6)
9.4 Sulfur-containing reductants	307	(5)
9.5 Low oxidation state metal ions	312	(2)
9.6 Tertiary phosphines and phosphites	314	(10)
9.7 Other reductants	324	(5)
References	329	(10)
Chapter 10. BORON AND ALUMINUM HYDRIDES IN PREPARATIVE COORDINATION CHEMISTRY	339	(29)
10.1 Applications of boron and aluminum hydrides in the synthesis of metal hydrides	340	(5)
10.2 Reduction without formation of M-H bonds	345	(2)
10.3 Application of hydrides as reductants for coordinated carbonyl ligands	347	(7)
10.4 Reactions of boron and aluminum hydrides with unsaturated hydrocarbyls and related ligands	354	(3)
10.5 Reactions of boron and aluminum hydrides with other coordinated ligands	357	(5)
References	362	(6)
Chapter 11. MOLECULAR REARRANGEMENTS OF COORDINATION COMPOUNDS	368	(24)
11.1 Rearrangements involving changes in metal-ligand binding sites	368	(4)
11.2 Rearrangements involving changes in coordination polyhedra	372	(5)
11.3 Rearrangement of coordinated ligands on a metal framework	377	(2)
11.4 Rearrangement of n-olefin complexes to o-organometallics	379	(4)
11.5 Rearrangement of acyl ligands to alkyl and carbonyl ligands	383	(1)
11.6 Interligand oxygen transfer	384	(1)
11.7 Conversion of phosphite complexes to phosphonate complexes	385	(2)
References	387	(5)
Chapter 12. SOLID STATE THERMAL SYNTHESIS OF COORDINATION COMPOUNDS	392	(29)
12.1 The Anderson rearrangement	392	(4)
12.2 Dehydration and deaquation	396	(3)
12.3 Syntheses involving abstraction of amine and other neutral ligands	399	(3)
12.4 Solid State thermal polymerization	402	(2)
12.5 Syntheses that involve deprotonation of a coordinated ligand followed by ring-closure	404	(2)
12.6 Thermal deprotonation of coordinated ammine ligands	406	(1)
12.7 Solid state cyclometallation	407	(3)
12.8 Thermal decarboxylation and disproportionation	410	(1)
12.9 Solid state thermal oxidation of tertiary phosphines	411	(1)
12.10 Solid state geometric isomerization	412	(3)
References	415	(6)
Conclusions	421	(2)
Index	423