Homogeneous catalysis with metal complexes: kinetic aspects and mechanisms
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Chichester
Wiley
2012
|
| Ausgabe: | 1. publ. |
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis Klappentext |
| Beschreibung: | Includes bibliographical references and indexes |
| Beschreibung: | XX, 806 S. graph. Darst. |
| ISBN: | 9780470666999 |
Internformat
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| 100 | 1 | |a Temkin, Oleg N. |e Verfasser |0 (DE-588)1023243806 |4 aut | |
| 245 | 1 | 0 | |a Homogeneous catalysis with metal complexes |b kinetic aspects and mechanisms |c O.N. Temkin ; translated from the Russian by P. P. Pozdeev |
| 250 | |a 1. publ. | ||
| 264 | 1 | |a Chichester |b Wiley |c 2012 | |
| 300 | |a XX, 806 S. |b graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 500 | |a Includes bibliographical references and indexes | ||
| 650 | 4 | |a Catalysis | |
| 650 | 4 | |a Metal catalysts | |
| 650 | 4 | |a Metal complexes | |
| 650 | 0 | 7 | |a Homogene Katalyse |0 (DE-588)4160579-2 |2 gnd |9 rswk-swf |
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Datensatz im Suchindex
| _version_ | 1804149091278520320 |
|---|---|
| adam_text | Contents
Notations
and Abbreviations
x¿
Preface to English Edition
хх,ц
Preface xix
Acknowledgments xx[
About the Author
ххщ
Introduction
1
1
State-of-the-Art in the Theory of Kinetics of Complex Reactions
21
1.1
Main concepts of the Horiuti-Temkin theory of steady-state reactions
21
1.1.1
Reaction mechanism: Stoichiometry and routes
22
1.1.2
Kinetics: Reaction rates with respect to substances and over routes
32
1.1.3
Kinetic polynomial
42
1.1.4
Determining the number of independent parameters in a kinetic model. The problem
of identifiability of parameters
44
1.2
Quasi-steady-state and quasi-equilibrium approximations in chemical kinetics
47
1.2.1
Theoretical criteria of quasi-steady-state intermediate concentrations
and quasi-equilibrium steps
49
1.2.2
Experimental criteria of applicability of quasi-steady-state approximation in various
systems
60
1.3
Methods of graph theory in chemical kinetics and in theory of complex reaction mechanisms
62
1.3.1
Linear mechanisms
62
1.3.2
Nonlinear mechanisms
71
1.3.3
Other fields of application of kinetic and bipartite graphs in chemical kinetics and
in theory of complex reaction mechanisms
76
1.4
Elementary steps
-
Selection rules
79
1.4.1
Main postulates, laws, and principles
79
1.4.2
Energy selection rules for elementary steps
88
1.4.3
Quantum-chemical selection rules for elementary steps
92
1.4.4
Topological selection rules for elementary steps
108
References
113
2
Complexity Functions of Catalysts and Reactants in Reactions Involving Metal
Complexes
121
2.1
Mononuclear metal complexes
122
2.1.1
Complexity functions: variants I and II
134
2.1.2
Complexity functions: variants III and IV
149
2.1.3
General problems and recommendations
165
viii Contents
2.2
Polynuclear
complexes in homogeneous catalytic and noncatalytic reactions
167
2.2.1
Systems with formation of associates
168
2.2.2
Systems with mononuclear and polynuclear complexes of various types
182
2.3
Catalysis with polynuclear copper(I) halide complexes in superconcentrated solutions
193
2.3.1
Coppe^I) chloride complexes in solution and in crystalline state
194
2.3.2
Kinetics of catalytic reactions of alkynes in concentrated NtLtCl-CuCl
aqueous solutions at constant complexity functions Feu and Fq
203
2.3.3
Determination of compositions of catalytically active copper(I) complexes
in various reactions
210
2.3.4
Studying
π
and
σ
complexes of copperCI) with alkynes in crystalline state
and in solution
216
2.3.5
Mechanisms of acetylene dimerization and hydrocyanation reactions.
Crystallochemical aspects
227
References
231
3
Multi-Route Mechanisms in Reactions Involving Metal Complexes
239
3.1
Factors accounting for the appearance and kinetic features of multi-route mechanisms
239
3.2
Analysis of multi-route reaction kinetics
246
3.3
Conjugation nodes and artificial multi-route character
271
3.4
Conjugate processes
304
3.4.1
Classical approach
305
3.4.2
Kinetic and thermodynamic conjugation in consecutive reactions
309
3.4.3
Conjugation in chain reactions
317
3.4.4
Conclusions
323
References
328
4
Polyfunctional Catalytic Systems
335
4.1
Oxidation reactions of organic and inorganic compounds
341
4.1.1
Oxidation of alkenes
341
4.1.2
Oxidation of 1,3-dienes
356
4.1.3
Oxidation of alkynes and
arenes
366
4.1.4
Oxidation of inorganic compounds
369
4.2
Reactions of chlorination and oxidative chlorination of organic compounds
372
4.2.1
Oxidative chlorination of alkynes
372
4.2.2
Oxidative chlorination of 1,3-dienes
384
4.2.3
Polyfunctional catalytic systems in chlorination reactions
386
4.3
Oxidative carbonylation of organic compounds
389
4.3.1
Oxidative carbonylation of HY molecules (Y
=
OR, OPh, NR2,
Ar, Alk) 390
4.3.2
Oxidative carbonylation of alkenes, dienes, and alkynes
400
4.4
Additive carbonylation of alkynes, alkenes, dienes, and alcohols
408
4.5
Substitution and addition reactions in alkyne chemistry
412
4.6
General problems in PFCS theory and practice
423
4.6.1
PFCSs and principles of their functioning
423
4.6.2
Kinetic and chemical functions of p-benzoquinone and other
quiñones
in PFCSs
426
4.6.3
Variants of association of catalytic reactions and catalytic systems
436
References
442
Contents ix
5
Mechanisms of Formation of Catalytically Active Metal Complexes
453
5.1
Main stages of catalytic process
454
5.2
Chemical reactions involved in the formation of active centers
457
5.3
Mechanisms of active center formation in particular processes
468
5.3.1
Mechanisms of active metal complex formation in PdBra-LiBr-PiOPh^
-Mr¬
zí
-CztHg OH catalytic system for aery late synthesis
468
5.3.2
Carbene metal complexes in metathesis of olefins and analogous processes
471
5.3.3
Mechanisms of 1-butene isomerization in Ni[P(OEt)3]4-H2SO4-MeOH system
488
5.3.4
Features of the formation and decay of active centers in acrylic derivatives synthesis
by the Reppe Method
490
5.3.5
Protecting active centers by catalytic process from destruction
492
5.3.6
Mechanism of active center formation in Pd(OAc)2-PPh3-p-benzoquinone-MeOH
catalytic system for alkyne oxidative carbonylation at sC-H bond
494
5.3.7
Catalysis with small palladium(I) halide and carbonyl halide clusters
499
5.3.8
Mechanisms of formation of large cluster complexes and microheterogeneous
nanoparticles
507
5.3.9
Synthesis and characterization of giant palladium clusters
512
5.3.10
Approaches to identification of the nature of catalytically active species
in solutions of metal complexes
513
5.4
Examples of chain mechanisms and chain carriers of various natures
518
5.5
Classification of mechanisms of real catalytic processes
528
References
536
6
Nonlinear Effects (Critical Phenomena) in Reaction Dynamics
in Homogeneous Catalysis with Metal Complexes
545
6.1
Historical notes
548
6.2
Physicochemical factors responsible for the critical phenomena in homogeneous reactions
551
6.2.1
Thermodynamic features of nonequilibrium processes near and far from
equilibrium
552
6.2.2
Dynamic behavior of systems with linear mechanisms in open reactors with complete
mixing
565
6.2.3
Nonlinearity of kinetic models
570
6.2.4
Main principles and methods of analysis of the dynamic behavior of nonlinear
systems
573
6.3
Analysis of simple nonlinear kinetic models
582
6.4
Mechanisms of oscillatory catalytic reactions
630
6.4.1
Belousov-Zhabotinskii reaction (BZ reaction)
630
6.4.2
Liquid-phase oxidation of organic compounds by oxygen in
Со(ОАс)т-Вг-
СНзСООН
system
640
6.4.3
Oxidative carbonylation of alkynes in solutions of palladium complexes
644
References
658
7
Rational Strategy for Designing Kinetic Models and Studying Complex Reaction
Mechanisms
665
7.1
Stages in the development of chemical kinetics and methodological aspects of the strategy
of studying complex reaction mechanisms
666
χ
Contents
7.2
Alternative strategies for studying complex reaction mechanisms and designing kinetic models
669
7.2.1
Traditional strategy
669
7.2.2
Rational strategy
671
7.3
Hypothesis generation methods and examples
674
7.4
Hypothesis generation programs: Application examples and related problems
677
7.4.1
Combinatorics on kinetic graphs
677
7.4.2
ChemComb (Comb
1)
program
686
7.4.3
MECHEM
program
691
7.4.4
NetGen program
694
7.4.5
TAMREAC program
697
7.4.6
ChemNet program
697
7.4.7
Large reaction networks and problems in discrimination of hypotheses
and construction of compact kinetic models
713
References
733
8
Effect of Medium on Reaction Rates in Homogeneous Catalysis with Metal Complexes
741
8.1
Effect of electrolytes on the activity coefficients of reaction medium components
743
8.2
Effect of electrolytes on the solubility of nonelectrolytes (gases and organic compounds)
748
8.3
Effect of electrolytes on the rates of elementary reactions between ions and uncharged
substrates
752
8.4
Kinetics of catalytic reactions in concentrated aqueous electrolyte (HC1) solutions
754
8.5
Organic solvents in homogeneous catalysis with metal complexes
760
8.5.1
Main physical and chemical properties of solvents
760
8.5.2
Association of solvents and formation of molecular complexes
763
8.5.3
Metal complexes in organic and aqueous-organic solvents
765
8.5.4
Ion association, ion pairs, and specific salt effect in organic solvents
771
8.6
Strong
protonie
acids in organic solvents and kinetics of catalytic reactions with metal
complexes in these media
775
8.6.1
Structure and properties of strong acid solutions in organic solvents
776
8.6.2
Kinetics of catalytic reactions in HC1-NMP,
НСІ-Сг^ОН,
and
HCI-C2H5OH-CH3CN systems
783
8.7
Ionic liquids in catalytic chemistry
787
References
79
1
Conclusion
797
Subject Index
801
Index of Metals
803
Index of Reactions
805
HOMOGENEOUS
CATALYSIS
WITH METAL
COMPLEXES
Kinetic Aspects and Mechanisms
OLEG
N.
TEMKIN, Department of Chemistry and Technology of Basic Organic Synthesis,
M. V. Lomonosov Moscow State University of Fine Chemical Technology, Moscow, Russia
Translated by P. P. POZDEEV
oluble metal complexes has gained considerable attention due to its
unique applications and features such as high activity and selectivity. Catalysis of this type has
demonstrated impressive achievements in synthetic organic chemistry and commercial
chemical technology.
Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms presents a
comprehensive summary of the results obtained over the last sixty years in the field of the
kinetics and mechanisms of organic and inorganic reactions catalyzed with metal complexes.
Topics covered include:
•
Specific features of catalytic reaction kinetics in the presence of various mono-
and polynuclear metal complexes and nanoclusters
•
Multi-route mechanisms and the methods of their identification, as well as
approaches to the kinetics of polyfunctional catalytic systems
•
Principles and features of the dynamic behavior of nonlinear kinetic models
•
The potential, achievements and limitations of applying the kinetic approach to
the identification of complex reaction mechanisms
•
The development of a rational strategy for designing kinetic models
•
The kinetic models and mechanisms of many homogeneous catalytic processes
employed in synthetic and commercial chemistry
Written for specialists in the field of kinetics and catalysis, this book is also relevant for
post-graduates engaged in the study of catalysis with metal complexes and complex
reaction kinetics.
ISBN
978-0-470-66699-9
©WILEY
wilev.com
9
«780470»666999
|
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| ctrlnum | (OCoLC)796219091 (DE-599)BVBBV040127796 |
| discipline | Chemie / Pharmazie Physik Chemie |
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| id | DE-604.BV040127796 |
| illustrated | Illustrated |
| indexdate | 2024-07-10T00:17:31Z |
| institution | BVB |
| isbn | 9780470666999 |
| language | English |
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| physical | XX, 806 S. graph. Darst. |
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| spelling | Temkin, Oleg N. Verfasser (DE-588)1023243806 aut Homogeneous catalysis with metal complexes kinetic aspects and mechanisms O.N. Temkin ; translated from the Russian by P. P. Pozdeev 1. publ. Chichester Wiley 2012 XX, 806 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Includes bibliographical references and indexes Catalysis Metal catalysts Metal complexes Homogene Katalyse (DE-588)4160579-2 gnd rswk-swf Metallkomplexe (DE-588)4038898-0 gnd rswk-swf Homogene Katalyse (DE-588)4160579-2 s Metallkomplexe (DE-588)4038898-0 s DE-604 Digitalisierung UB Bayreuth application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=024985039&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis Digitalisierung UB Bayreuth application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=024985039&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA Klappentext |
| spellingShingle | Temkin, Oleg N. Homogeneous catalysis with metal complexes kinetic aspects and mechanisms Catalysis Metal catalysts Metal complexes Homogene Katalyse (DE-588)4160579-2 gnd Metallkomplexe (DE-588)4038898-0 gnd |
| subject_GND | (DE-588)4160579-2 (DE-588)4038898-0 |
| title | Homogeneous catalysis with metal complexes kinetic aspects and mechanisms |
| title_auth | Homogeneous catalysis with metal complexes kinetic aspects and mechanisms |
| title_exact_search | Homogeneous catalysis with metal complexes kinetic aspects and mechanisms |
| title_full | Homogeneous catalysis with metal complexes kinetic aspects and mechanisms O.N. Temkin ; translated from the Russian by P. P. Pozdeev |
| title_fullStr | Homogeneous catalysis with metal complexes kinetic aspects and mechanisms O.N. Temkin ; translated from the Russian by P. P. Pozdeev |
| title_full_unstemmed | Homogeneous catalysis with metal complexes kinetic aspects and mechanisms O.N. Temkin ; translated from the Russian by P. P. Pozdeev |
| title_short | Homogeneous catalysis with metal complexes |
| title_sort | homogeneous catalysis with metal complexes kinetic aspects and mechanisms |
| title_sub | kinetic aspects and mechanisms |
| topic | Catalysis Metal catalysts Metal complexes Homogene Katalyse (DE-588)4160579-2 gnd Metallkomplexe (DE-588)4038898-0 gnd |
| topic_facet | Catalysis Metal catalysts Metal complexes Homogene Katalyse Metallkomplexe |
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