Chemical Kinetics and Inorganic Reaction Mechanisms

kinetic isotope effect of sulfur-34.- 1.14.1.2. Isotope effects and the mechanism of enzymatic catalysis.- 1.14.2. Secondary kinetic isotope effects.- 1.14.2.1. Secondary ß-deuterium kinetic isotope effect.- 1.14.2.2. Secondary ?-deuterium kinetic isotope effect.- 1.15. Influence of tunneling on the primary and secondary kinetic isotope effects.- 1.15.1. Extremely high kinetic isotope effects and tunneling.- 1.15.2. Secondary ?-deuterium kinetic isotope effect and tunneling.- 1.15.2.1. Reaction branching and extreme kinetic isotope effects.- References.- 2. Substitution reactions on metal complexes.- 2.1. Introduction.- 2.2. Reactions of organometallic complexes with halogenes (SE2 mechanism).- 2.3. Labile and inert complexes.- 2.4. Crystal-field theory.- 2.4.1. Splitting of d orbitals in the octahedral crystal field.- 2.4.2. Crystal-field stabilization energies of d orbitals for various geometric configurations, and substitution rates.- 2.4.3. Influence of crystal field stabilization energies on the rates and mechanism of octahedral substitutions.- 2.5. Ligand field and electron transitions.- 2.6. Substitution reactions on octahedral complexes.- 2.6.1. Rates of water exchange in octahedral aqua complexes.- 2.6.2. Pressure dependence of the reaction rate constant; volume of activation.- 2.6.3. Substitution of coordinated water of octahedral complexes with anions ("anations").- 2.6.4. Aquation and acid catalysis.- 2.6.5. Base catalysis.- 2.6.6. Stereochemistry of octahedral substitutions.- 2.6.7. Attacks of reactants on ligands (not on metal).- 2.6.8. Linkage isomerism.- 2.7. Nucleophilicity in inorganic chemistry.- 2.7.1. npt Scale.- 2.7.2. The scale of Swain and Scott.- 2.7.3. Edwards' scale.- 2.7.4. The theory of "hard" and "soft" acids and bases.- 2.8. Substitutions on square-planar complexes.- 2.8.1. The mechanism of ligand replacements.- 2.8.2. Trans effect.- 2.8.3. Cis effect.- 2.8.4. Leaving group effects.- 2.8.5. Effect of the central metal ion.- 2.9. Substitution reactions of tetrahedral complexes.- 2.10. Substitutions of carbonyls.- 2.10.1. Substitutions of the carbonyls of complexes with a metal-metal bond.- References.- 3. Oxidative additions and reductive eliminations.- 3.1. Oxidative additions.- 3.1.1. Two-electron oxidative additions.- 3.1.1.1. Mechanism of oxidative addition of the nucleophilic substitution type.- 3.1.2. One-electron oxidative additions.- 3.2. Reductive eliminations.- References.- 4. Molecular nonrigidity.- 4.1. Pseudorotation.- 4.2. Nonrigidity of metal carbonyls.- 4.3. [(Fulvalene)tetracarbonyldimthenium]. Storage of light energy.- References.- 5. Electron-transfer reactions.- 5.1. Introduction.- 5.2. Franck-Condon principle.- 5.3. Outer-sphere electron transfer.- 5.3.1. Marcus theory of outer-sphere electron transfer.- 5.3.2. Long-range electron transfers in biological systems.- 5.4. Inner-sphere electron transfer.- 5.5. Reactions with solvated electrons.- References.- 6. Reactions of free radicals.- 6.1. Chain reactions.- 6.2. Stability of the metal-carbon ? bond.- 6.3. Oxidation of transition metal complexes by hydroxyl radicals.- 6.4. Reduction of transition metal complexes by organic radicals.- References.- 7. Mechanism of vitamin B12 action.- 7.1. Introduction.- 7.2. Mechanism of vitamin B12 activity.- 7.3. Difficulties in distinguishing D and Id mechanisms.- References.- 8. Kinetics and mechanisms of metalloporphyrin reactions.- 8.1. Introduction.- 8.2. Mechanism of metal incorporation into the porphyrin complex.- 8.3. Metalloporphyrins as oxygen carriers.- 8.4. Substitutions on metalloporphyrins.- 8.4.1. Imidazole, an essential component of many biological systems; the nature of metal bonding.- 8.4.2. Comparison of the bonding modes of imidazole and pyridine to a metal.- 8.5. Nature of the bond of amine ligands to cobalt(III) in porphyrins; the relation of ? to ? bonding.- 8.6. Catalytic action of metalloporphyrins.- 8.7. Why only porphyrins, but not their isomers, in nature.- 8.8. Nitrosoamine complex of metalloporphyrin, a probable intermediate in the mechanism of nitrosoamine activation of cancer.- 8.9. The sequence of bonded metalloporphyrins - a molecular photonic wire.- 8.10. Metalloporphyrins, metallophthalocyanines and analogous complexes in photodynamic therapy of cancer.- 8.10.1. Introduction.- 8.10.2. Red light for photodynamic therapy: metallotexaphyrins of lutetium and gadolinium as photosensitizers in cancer therapy.- 8.11. Some models of metalloenzymes.- References.- 9. Metallocenes, strong electron donors.- 9.1. Introduction.- 9.2. Bonding in the [?5-(C5H5)2Fe] complexes.- 9.3. Stability of ?-metallocenyl carbocations.- 9.4. Secondary ?-deuterium kinetic isotope effect and the structure of ferrocenylmethyl carbocation type transition state.- 9.4.1. High secondary ?-deuterium kinetic isotope effects for the primary carbon-oxygen cleavage in formolysis and acetolysis of dideuterioferrocenylmethyl benzoate.- 9.4.2. Possible contribution of tunneling to the high secondary ?-deuterium kinetic isotope effect.- 9.5. Ferrocene ability to stabilize a carbenium ion.- 9.5.1. Solvent variations and the rates of ferrocenylmethyl ester solvolyses.- 9.5.2. Relative rates of ferrocenylmethyl benzoate solvolyses in formic and acetic acid.- 9.6. Antitumor activity of metallocenes.- 9.7. Ferrocenes as nucleophilic catalysts can mediate kinetic resolution.- 9.8. Ferrocenes and molecular recognition.- 9.9. Metal-metal interactions in linked metallocenes.- 9.9.1. Metallocene derivatives.- 9.9.2. Concluding remarks.- References.- 10. Metal complexes in tumor therapy.- 10.1. Introduction.- 10.1.1. Chemotherapy of cancer.- 10.2. Complexes of the cis-PtL2X2 type as antitumor agents.- 10.3. Second generation of cisplatin analogs.- 10.3.1. The mechanism of antitumor activity of cisplatin.- 10.4. Gold complexes as antitumor agents.- 10.5. Antitumor activity of organogermanium compounds.- References.- 11. Heterogeneous and homogeneous catalysis by metals and transition metal complexes.- 11.1. Introduction.- 11.2. Heterogeneous catalysis by metals and metal oxides.- 11.3. Homogeneous catalysis by transition metal complexes.- 11.3.1. Hydroformylation of unsaturated compounds.- 11.3.2. Hydrocyanation of alkenes.- 11.3.3. Polymerization of alkenes and alkynes; Ziegler-Natta catalysts.- References.- 12. Chemical and biological nitrogen fixation.- 12.1. Introduction.- 12.2. Biological nitrogen fixation.- 12.2.1. Nitrogen fixation in bacteria.- 12.3. Reactions of N2 with transition metal complexes.- References.- 13. Cascade molecules (dendrimers).- 13.1. Introduction.- 13.2. Methods of dendrimer preparation.- References.- 14. Metal complexes with short memory effect.- 14.1. Introduction.- 14.2. Magnetic materials and information storage.- 14.3. Hyperthermy treatment of some tumors.- References.- 15. Some recent publications in the scientific spotlight.- 15.1. Introduction.- 15.2. C-Binding vs. N-binding of imidazoles to metal fragments.- References (section 15.2).- 15.3. Hexaphyrin, an expanded porphyrin ligand for the U022+ and NpO2+ coordination.- References (section 15.3).- 15.4. Alkane picosecond carbon-hydrogen bond cleavage at the iridium carbonyl center.- References (section 15.4).- 15.5. Photochemical activation of the N?N bond in a dimolybdenum-dinitrogen complex.- References (section 15.5).- 15.6. Separation and purification of olefins using dithiolene complexes.- References (section 15.6).- 15.7. Highly efficient ring-opening metathesis polymerization (ROMP).- References (section 15.7).- 15.8. Supramolecular cluster catalysis: benzene hydrogenation catalyzed by a cationic triruthenium cluster.- References (section 15.8).- 15.9. A trimer of zinc(II), ruthenium(II), and tin(IV) porphyrins called the trinity of metals.- References (section 15.9).- 15.10. Bis(l,2,3,4?4-anthracene)cobaltate(1-).- References (section 15.10).- 15.11. sp-Carbon chains surrounded by sp3-carbon double helices: a class of molecules accessible by self-assembly and models for "insulated" molecular-scale devices.- References (section 15.11).- 15.12. Ferrocene and fullerene hybrid.- References (section 15.12).- Epilogue.- Physical and chemical constants.- Conversion factors.- Some often used abbreviations.- Prefixes.- Electronic configurations of the elements.