Fragment-oriented design of catalysts [Elektronische Ressource] : a theoretical study on bond activation / vorgelegt von Axel Diefenbach

Informations

• Publié par: philipps-universitat_marburg
• Publié le: 01 janvier 2004
• Nombre de lectures: 14
• Langue: English
• Poids de l'ouvrage: 2 Mo

Extrait

Fragment-Oriented Design of Catalysts
A Theoretical Study on Bond Activation


Dissertation

zur

Erlangung des Doktorgrades
der Naturwissenschaften
(Dr. rer. nat.)


dem Fachbereich Chemie
der Philipps-Universität Marburg

vorgelegt von

Axel Diefenbach

aus Ludwigshafen


Marburg/Lahn, 7.12.2000























Vom Fachbereich Chemie der Philipps-Universität Marburg als Dissertation
angenommen am __________.



Erstgutachter: Prof. Dr. Gernot Frenking
Zweitgutachter: Univ.-Doz. Dr. F. Matthias Bickelhaupt


Datum der Promotion: 20.12.2000.
Prolegomenon I




Credo ut intelligam



















The time necessary to create a dissertation is both a time of scientific work and personal
development. I would like to thank those persons who have accompanied me during this
period.
My scientific progress is primarily due to F. Matthias Bickelhaupt who initialized
this work and provided several useful ideas. Furthermore, he taught me to concentrate
on those things which are most important for a scientific understanding. Scientifically
important impulses came also from Gernot Frenking, whom I would like to thank for his
collaboration.
Great impact on my personal development had Jochen Röpke to whom I am very
grateful for suggesting a fundament on which a whole branch of thoughts, aims and
attitudes have grown. The latter were significantly influenced by Frank Kuhnecke. II

Contents III

Contents

1 Introduction 1
1.1 Culture, Chemistry and Catalysis 1
1.2 Fragment-Oriented Design of Catalysts 3
1.3 Outline 6
1.4 References 7

2 Methods 9
2.1 Density Functional Theory 9
2.2 Relativity 11
2.3 Bond Analysis 14
2.4 References 17

3 The Nature of the Transition Metal–Carbonyl Bond 19
3.1 Introduction 20
3.2 Methods 26
3.3 Results and Discussion 27
3.4 Conclusions 44
3.5 References 46

4 Relativistic Effects in Metal-Catalyzed Bond Activation 51
4.1 Introduction 52
4.2 Methods 54
4.3 Results and Discussion 58
4.4 Conclusions 76
4.5 References 77



IV Contents





5 Activation of H–H, C–H, C–C and C–Cl Bonds by Pd(0). 83
5.1 Introduction 84
5.2 Methods 86
5.3 Results and Discussion 88
5.4 Conclusions 99
5.5 References 101

6 The Mechanism of Anion Assistance. 107
6.1 Introduction 108
6.2 Methods 111
6.3 Results and Discussion 112
6.4 Conclusions 130
6.5 References 131

7 Toward Fragment-Oriented Design of Catalysts 137
7.1 Introduction 138
7.2 Methods 139
7.3 Results and Discussion 141
7.4 Conclusions 149
7.5 References 151

8 Summary 157
Zusammenfassung 164


List of abbreviations V
List of Abbreviations

ADF Amsterdam Density Functional
ATS Activation strain-Transition State interaction model of chemical
reactivity
B88 Becke-88 nonlocal exchange energy functional
BDE Bond Dissociation Energy
CDA Charge Decomposition Analysis
DFT Density Functional Theory
DZP Double– basis set with one Polarization function
ETS Extended Transition State method
GGA Generalized Gradient Approximation
KS Kohn–Sham
LDA Local Density Approximation
MEP Minimum Energy Path
MO Molecular Orbital
P86 Perdew-86 nonlocal correction energy functional
QR Quasirelativistic
SCF Self-Consistent Field
STO Slater-Type Orbital
TS Transition State
TZP Triple– basis set with one polarization function
TZ2P Triple– basis set with two polarization functions
TZ(2)P Triple– basis set with two polarization functions on H, C, O, Cl, I
and one polarization function on Pd
VWN Local correlation energy functional based on the Vosko–Wilk–Nusair
parameterization
ZORA Zeroth-Order Regular Approximation

zzzzVI





Fragment-Oriented Design of Catalysts
A Theoretical Study on Bond Activation


Dissertation

zur

Erlangung des Doktorgrades
der Naturwissenschaften
(Dr. rer. nat.)


dem Fachbereich Chemie
der Philipps-Universität Marburg

vorgelegt von

Axel Diefenbach

aus Ludwigshafen


Marburg/Lahn, 7.12.2000























Vom Fachbereich Chemie der Philipps-Universität Marburg als Dissertation
angenommen am __________.



Erstgutachter: Prof. Dr. Gernot Frenking
Zweitgutachter: Univ.-Doz. Dr. F. Matthias Bickelhaupt


Datum der Promotion: 20.12.2000.