Chemical Kinetics and Inorganic Reaction Mechanisms (2 Revised)

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Chemical Kinetics and Inorganic Reaction Mechanisms (2 Revised)

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  • 製本 Hardcover:ハードカバー版/ページ数 380 p.
  • 言語 ENG
  • 商品コード 9780306477478
  • DDC分類 541.394

Full Description

The serious study of the reaction mechanisms of transition metal com­ plexes began some five decades ago. Work was initiated in the United States and Great Britain; the pioneers ofthat era were, inalphabetical order, F. Basolo, R. E. Connick, 1. O. Edwards, C. S. Garner, G. P.Haight, W. C. E. Higgision, E.1. King, R. G. Pearson, H. Taube, M.1. Tobe, and R. G. Wilkins.A larger community of research scientists then entered the field, many of them stu­ dents ofthose just mentioned. Interest spread elsewhere as well, principally to Asia, Canada, and Europe. Before long, the results ofindividual studies were being consolidated into models, many of which traced their origins to the better-established field of mechanistic organic chemistry. For a time this sufficed, but major revisions and new assignments of mechanism became necessary for both ligand sub­ stitution and oxidation-reduction reactions. Mechanistic inorganic chemistry thus took on a shape of its own. This process has brought us to the present time. Interests have expanded both to include new and more complex species (e.g., metalloproteins) and a wealth of new experimental techniques that have developed mechanisms in ever-finer detail. This is the story the author tells, and in so doing he weaves in the identities of the investigators with the story he has to tell. This makes an enjoyable as well as informative reading.

Contents

1. Chemical kinetics and reaction mechanisms.- 1.1. Introduction.- 1.2. Chemical reactions and energy changes.- 1.3. Collision theory.- 1.3.1. Calculation of rate constants.- 1.3.2. Arrhenius equation.- 1.4. Transition state theory.- 1.5. Steric effects and reactivity of strictly oriented molecules.- 1.5.1. Molecular beams studies.- 1.5.2. Symmetric top molecules.- 1.6. Reaction energy profiles and the reaction coordinate.- 1.7. Bimolecular and unimolecular nucleophilic substitutions (SN2 and SN1 substitutions).- 1.8. Novel views on the mechanism of bimolecular substitutions in the gas phase.- 1.9. Classification of reaction mechanisms in inorganic chemistry involving metal complexes (D, A, Id and Ia mechanisms).- 1.9.1. The collision theory in solutions.- 1.9.2. Primary kinetic salt effect.- 1.9.3. IUPAC recommendations for the representation of reaction mechanisms.- 1.9.4. Nomenclature of coordination compounds.- 1.10. Direct observation of the activated complex.- 1.10.1 Spectroscopy in the transition state region.- 1.11. The influence of the solvent on the reaction rates and mechanisms.- 1.11.1. Influence of solvent polarity on the rates of chemical reactions.- 1.11.1.1. Entropy change in charge separation.- 1.11.1.2. The effect of solvents on reaction rates.- 1.11.1.3. The ionizing power of solvents.- 1.11.1.4. Ionic strength of the medium and the reaction rate.- 1.11.1.5. Linear free energy relationships.- 1.11.1.6. Solvent nucleophilicity and definition of the nucleophilic constant N.- 1.11.1.7. Solvent coordinating property and electron-donor ability.- 1.11.1.8. Drastic acceleration of the oxidation of hexacyanoferrate(II) in solvents, strong electron donors.- 1.11.1.9. The dissociative type reaction may not depend on solvent polarity.- 1.12. Steady-state approximation and its application to replacement reactions.- 1.13. Reactions of ion pairs.- 1.14. Primary and secondary kinetic isotope effects.- 1.14.1. Primary kinetic isotope effects.- 1.14.1.1. Primary 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.