Structure and reactivity of solvated transition metal ions and complexes [Elektronische Ressource] / vorgelegt von Anita Lagutschenkov

Anita Beni

Informations

• Publié par: technische_universitat_kaiserslautern
• Publié le: 01 janvier 2008
• Nombre de lectures: 28
• Langue: Deutsch
• Poids de l'ouvrage: 5 Mo

Extrait

Technische Universität Kaiserslautern
Fachbereich Chemie


Structure and reactivity of solvated
transition metal ions and complexes


Am Fachbereich Chemie der Technischen Universität Kaiserslautern
zur Erlangung des akademischen Grades „Doktor der Naturwissenschaften“
genehmigte

Dissertation
(D386)


vorgelegt von
Dipl.-Chem. Anita Lagutschenkov



Betreuer: Prof. Dr. G. Niedner-Schatteburg


Tag der wissenschaftlichen Aussprache: 22. September 2008



























Die vorliegende Arbeit wurde in der Zeit von Juli 2003 bis August 2008 im Fachbereich
Chemie der Technischen Universität Kaiserslautern unter der Betreuung von Prof. Dr. G.
Niedner-Schatteburg angefertigt.







Datum des Antrags auf Eröffnung des Promotionsverfahrens: 08.01.2007
Tag der wissenschaftlichen Aussprache: 22.09.2008















Promotionskommission:
Vorsitzender: Prof. Dr.-Ing. S. Ernst
1. Berichterstatter: Prof. Dr. G. Niedner-Schatteburg
2. Berichterstatter: Prof. Dr. M. Gerhards




















O glücklich, wer noch hoffen kann,
aus diesem Meer des Irrtums aufzutauchen!
Was man nicht weiß, das eben brauchte man,
und was man weiß, kann man nicht brauchen. (Faust)
Goethe
Faust 1, Vor dem Tor






I

Contents

0. Abbreviations III
1. Introduction 1
2. Methods 7
2.1 Experimental methods 7
2.1.1 Ion generation: Electrospray ionization and laser vaporization 7
2.1.3 Infrared multiphoton dissociation spectroscopy with the free electron laser at the
Centre Laser Infrarouge Orsay 21
2.2 Theoretical methods 24
2.3 References 33
3. The spectroscopic signature of the "all-surface" to "internally solvated" structural
transition in water clusters in the n=17 −21 size regime 37
3.1 Introduction 37
3.2 Summary of the results 39
3.3 Conclusions 43
3.5 References 45
+4. Infrared spectrum of NH (H O): Evidence for mode specific fragmentation 47 4 2
4.1 Introduction 48
4.2 Summary of the results 49
4.3 References 55
5. Beyond the harmonic approach: Calculation of anharmonic frequencies of protonated
and deprotonated carboxylic acid homologues, from oxalic acid to adipic acid 57
5.1 Introduction 57
5.2 Computational details 60
5.3 Results and discussion of the computational results 61
5.4 Summary and conclusions 78
5.5 References 79 II
6. Preliminary experimental and quantum chemical studies for IRMPD and IR matrix
isolation spectroscopy of dioxygen containing nonheme iron(III) catecholate complexes
81
6.1 Introduction 81
6.2 Measurements with ESI-FT-ICR-MS 83
6.3 Density functional calculations 88
6.4 Summary and outlook 97
6.5 References 99
7. Complexes of vanadium and vanadium oxides with organic solvents: FT-ICR-MS
study and IRMPD spectra compared to ab initio calculations 101
7.1 Introduction 101
7.2 Experimental details 102
7.3 Computational details 103
7.4 Results and Discussion 104
7.4.1 IRMPD spectra of vanadium oxide acetonitrile complexes 104
7.4.2 IRMPD spectra of oxide methanol complexes 117 vanadium oxide ethanol complexes 128
7.5 Summary and outlook 134
7.6 References 139
8. Energetics and reaction pathways of intramolecular reductive nitrile coupling of
monocationic group 3 through 7 transition metal acetonitrile complexes 143
8.1 Introduction 143
8.2 Computational details 146
8.3 Results and discussion 147
8.4 Summary and outlook 160
8.5 References 161
9. Summary 167
10. Zusammenfassung 171
11. List of Publications 175
12. Acknowledgment 177
13. Curriculum Vitae 179 III
Abbreviations


B3LYP Becke three parameter hybrid Lee Yang Parr correlation functional
BLYP Becke Lee Yang Parr correlation functional
CAD collision activated dissociation
CC coupled cluster
CCSD(T) coupled cluster with single and double and perturbative triple
excitations
CE capillary electrophoresis
CID collision induced dissociation
CGF contracted Gaussian function
CLIO Centre Laser Infrarouge d'Orsay
CPMD Car-Parrinello molecular dynamics
DFT density functional theory
DZVP double-zeta valence plus polarization
ECP effective core potential
ESI electrospray ionization
FEL free electron laser
FFT fast Fourier transform
FT −ICR −MS Fourier transform ion cyclotron resonance mass spectrometry
FWHM full width at half maximum
GGA generalized gradient approximation
GTO Gaussian-type orbital
HF Hartree-Fock
HPLC high performance liquid chromatography
HWHM half width at half maximum
IR infrared
IRMPD infrared multiphoton dissociation
IVR internal vibrational relaxation
LDA local density approximation
LVAP laser vaporization (source)
MALDI matrix assisted laser desorption ionization
MD molecular dynamics
MICRA mobile ion cyclotron resonance analyzer

 IV
MP2 second order Møller-Plesset perturbation theory
MS mass spectrometry
PA proton affinity
PEEK polyetheretherketone
PES potential energy surface
RF radio frequency
RI resolution of the identity
S/N signal to noise ratio
SCF self consistent field
SORI sustained off resonance irradiation
STO Slater-type orbital
Tp' trispyrazolylborate
TZVP triple-zeta valence plus polarization
UV ultraviolet
VIS visible
ZPE zero point energy