1 Introduction ................................................. 1
1.1 Types of Homogeneous Catalysis with Metal Complexes,
Their Advantages and Drawbacks .......................... 1
1.2 Perspectives of the Industrial Use of Homogeneous
Catalysis with Metal Complexes .......................... 5
References ................................................... 9
2 Homogeneous Redox Catalysis with Transition Metal Compounds
in Oxide and Peroxide Systems ............................... 11
2.1 General Principles of Catalytic Redox Reactions
with Metal Compounds ................................... 11
2.2 Intermediate Compounds, O2 Molecule Activation,
and Free Radicals in the Catalysis of Oxidation
Processes .............................................. 17
2.2.1 Nature of Forming Intermediate Compounds ........ 17
2.2.2 Oxygen Molecule Activation: Intermediate
Species, and Free Radicals ...................... 20
2.2.3 Peroxocomplexes of Some Metals .................. 43
2.3 Theoretical Aspects of Catalysis with Metal Complexes .. 46
2.3.1 Influence of Complex Formation on Metal Ion
Reactivity and Catalytic Processes Mechanisms
(Role of Coordination in Catalysis) ............. 46
2.3.2 Qualitative Model of the Theory of PCT
Complexes ....................................... 51
2.4 General Principles of Redox Catalysis Mechanisms
Determination .......................................... 54
2.4.1 Possible Mechanisms of Catalytic Redox Systems
Fez+aq-H2O2 and Fez+Ln-H2O2 ..................... 54
2.4.2 Stages of Revealing Catalytic Redox Reactions
Mechanism (Methodic Aspect2) .................... 62
2.5 Mechanisms of Oxide and Peroxide Systems Redox
Transformations Catalysis with Transition Metal
Compounds .............................................. 75
2.5.1 Mechanisms of O2 Transformation in Oxide
Catalytic Systems ............................... 75
2.5.2 Mechanisms of H2O2 Decomposition in the
Peroxide Catalytic Systems ...................... 80
2.6 Mechanisms of Organic Substrates (S) Oxidation
in Oxide and Peroxide Systems .......................... 91
2.6.1 Mechanisms of Organic Substrates Oxidation by
Oxygen [Systems Mz+(Mz+Ln)-O2-S] ................ 91
2.6.2 Mechanisms of Organic Substrate's Oxidation
by Hydrogen Peroxide [Systems
Mz+(Mz+Ln)-H2O2-S] .............................. 96
2.7 Ferryl Particles in the Catalysis of Oxidation
Processes ............................................. 105
2.7.1 Experimental Confirmation of Ferryl Particles
Formation ...................................... 105
2.7.2 Quantum-Chemical Methods of Ferryl (Manganyl)
Particles Formation Study ...................... 107
References ................................................. 113
3 Biochemical Processes and Metal Complexes'Role as
Catalysts .................................................. 123
3.1 Catalytic Influence of Transition Metal Compounds
on Biological Processes ............................... 123
3.1.1 Role of Transition Metal Ions in Biological
Systems ........................................ 124
3.1.2 Catalytic Reactions in the Initiation of
Lipid Peroxidation ............................. 128
3.1.3 Ligands Influence of Haber-Weiss Reaction ...... 133
3.1.4 Toxicity of O2 Reduced Forms with Regard to
Biological Systems and Methods of Protection ... 136
3.1.5 Role of Bleomycin and Its Models in DNA
Deterioration .................................. 142
3.1.6 Intermediates of Ferryl Particles Type in
Biochemical Systems ............................ 155
3.2 Enzymes and Their Modeling ............................ 161
3.2.1 Mechanisms of Some Enzymes' Functioning and
Their Modeling: Modeling of Monooxidases in
Alkanes, Alkenes, and Other Substrates
Hydroxylation and Epoxidation .................. 161
3.2.2 Dopamine β-Hydroxylase and Its Models .......... 203
3.2.3 Model Systems of Dioxygenases .................. 206
3.2.4 Model Systems of Catalase ...................... 212
3.2.5 Peroxidases and Their Model Systems ............ 219
3.2.6 Superoxide Dismutase and Its Models ............ 231
3.2.7 Models of Oxidases (Laccase, Cytochrome C,
and Galactose Oxidase) ......................... 236
References ................................................. 244
4 Catalytic Processes and Human Diseases ..................... 261
4.1 Catalytic Free Radical Processes In Vivo and
Toxicity of Oxygen Reduction Products ................. 261
4.2 Stress and Catalytic Processes ........................ 267
4.3 Inflammatory Processes and Role of Metal Compounds .... 279
4.4 Role of Enzymes and Metal Compounds in Phagocytosis ... 284
4.5 Metal-Catalyzed Oxidation and Ageing .................. 289
4.5.1 Oxidative Damage of Proteins and Enzymes, and
Ageing ......................................... 289
4.5.2 Mitochondria Damage with Free Radicals and
Ageing ......................................... 292
4.5.3 Mechanism of Lipofuscin Formation and Ageing ... 294
4.5.4 The Role of Antioxidant Enzymes and
Substances in Cellular Ageing .................. 295
4.6 Diseases of Joints and Tissues and Catalytic Free
Radical Processes ..................................... 299
4.7 Catalytic and Radical Processes on Atherosclerosis
and Myocardial Ischemia ............................... 301
4.7.1 Catalytic and Radical Processes on
Atherosclerosis ................................ 301
4.7.2 Myocardial Deteriorations and Catalytic
Processes with Free Radicals Formation ......... 307
References ................................................. 310
5 Catalytic Oxidation of Oxyacids and Natural Polyphenols .... 319
5.1 Metabolic Cycles of Tri- and Dicarbonic Acids ......... 319
5.2 Catalytic Processes of Dicarbonic Acids of Baroud
Cycle Transformations ................................. 322
5.2.1 Catalytic Processes of Baroud Cycle Oxyacids
Transformations ................................ 322
5.2.2 General Regularities of the Reduction-
Oxidation Conversions of the Baroud Cycle
Oxyacids ....................................... 338
5.3 Catalytic Transformations of Natural Polyphenols ...... 341
5.3.1 Role of Natural Polyphenols and Their
Catalytic Oxidative Transformations ............ 341
5.3.2 Catalysis of Catechins Oxidation with Oxygen
and Hydrogen Peroxide in the Presence of Fe3+
and Fe2+ Ions .................................. 342
References ................................................. 347
6 Catalytic Processes in Ecological Chemistry ................ 351
6.1 Ecological Chemistry and Catalysis with Metal
Complexes ............................................. 351
6.2 Catalytic Processes in the Atmosphere and Acid Rain
Formation ............................................. 355
6.3 Catalytic Redox Processes in Natural Water and Its
Self-Purification ..................................... 369
6.3.1 Main Sources of H2O2, OH•- and O2•-(HO2•)
Radicals Formation in Natural Water ............ 369
6.3.2 H2O2 and O2 Activation in Natural Water and
the Role of Metal Compounds .................... 374
6.3.3 Photocatalytic Transformation of Nitrogen
Mineral Forms in Water ......................... 381
6.3.4 Photocatalytic Transformations of
Anthropogenic Organic Pollutants in Water
Compartments ................................... 387
6.3.5 Modeling of Pollutant Transformation and
Self-purification Capacity of Natural Water .... 390
6.4 Wastewater Treatment and Catalytic Processes .......... 396
6.4.1 Principles of Catalytic Wastewater Treatment ... 396
6.4.2 Combined Redox-Photocatalytic Processes ........ 401
6.5 Catalymetry of Environmental Objects .................. 408
References ................................................. 415
7 Homogeneous Catalysis with Metal Complexes in the
Chemical Industry and Foodstuffs Chemistry ................. 423
7.1 Catalytic Processes in the Chemical Industry .......... 423
7.1.1 Catalytic Oxidation of Organic Compounds in
Model Systems and Their Possible Industrial
Applications ................................... 423
7.1.2 Catalytic Hydroxylation and Epoxidation
in Industrial Processes ........................ 426
7.1.3 Mechanisms of Some Industrial Catalytic
Processes ...................................... 434
7.2 Foodstuffs Chemistry and Catalysis .................... 438
7.2.1 Catalytic Lipids Peroxidation in Foodstuffs .... 438
7.2.2 Distribution of Iron Compounds in Foodstuffs
and Their Influence on Lipids Peroxidation ..... 446
7.2.3 Role of Antioxidants in Foodstuffs
Preservation ................................... 449
7.3 Redox Catalytic Processes in Wine-Making .............. 454
7.3.1 Redox Catalytic Non-Enzymatic Processes
During Wine Maturing and Ageing ................ 454
7.3.2 Methods of Wine Stabilization and Improving
of Its Organoleptic Properties ................. 457
References ................................................. 461
Index ......................................................... 467
|
