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Solid-state spin-1/2 NMR studies of disorder, bonding, and symmetry Open Access

Descriptions

Other title
Subject/Keyword
cyanide
coupling
DFT
gold
tensor
aurophilic
MO
Solids
platinum
NMR
antisymmetric
Dewar-Chatt-Duncanson
alkene
MAS
alkyne
shielding
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Harris, Kristopher J.
Supervisor and department
Roderick Wasylishen, Chemistry
Examining committee member and department
Daniel Leznoff, Chemistry, Simon Fraser University
Frank Hegmann, Physics
Wolfgang Jäger, Chemistry
Mariusz Klobukowski, Chemistry
Rik Tykwinski, Chemistry
Department
Department of Chemistry
Specialization

Date accepted
2009-06-09T20:50:45Z
Graduation date
2009-11
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
This thesis is concerned with applications of modern solid-state NMR spectroscopy. Investigations of three quite different types are undertaken, each of which attempt to advance knowledge in the fields of chemistry and NMR. The goal of each project is to obtain insight into the effects of chemical environment, in particular bonding, on the NMR observables. Carbon-13 and nitrogen-15 solid-state nuclear magnetic resonance has been used to study solid samples containing the dicyanoaurate(I) anion, [Au(CN)2]-, with n-butylammonium, potassium, and thallium counterions. Differences in Au-Tl metallophilic bonding are shown to cause a difference in the isotropic cyanide carbon-13 chemical shift of up to 15.7 ppm, while differences in Au-Au aurophilic bonding are found to be responsible for a change of up to 5.9 ppm. Disordered polymeric gold(I) monocyanide was also investigated, and a range of 7+-2% to 25+-5% of the AuCN chains are found to be "slipped" instead of aligned with the neighbouring chains at the metal position. An investigation of the chemical shift tensors of the 13C-labelled carbons in solid samples of Ph13C≡13CPh and (η2-Ph13C≡13CPh)Pt(PPh3)2·(C6H6) has also been carried out. Coordination of diphenylacetylene to platinum causes a change in the 13C chemical shift tensor orientation and a net increase in the isotropic chemical shift. The carbon chemical shift tensors in the platinum complex bear a striking similarity to those of the alkenyl-carbons in trans-Ph(H)C=C(H)Ph, and a theoretical discussion of these observations is presented. Each of the fundamental NMR interaction tensors (σ, J, D and V) may be decomposed into isotropic, symmetric, and antisymmetric components. Observations of all theoretically allowed components other than the antisymmetric portion of J (Janti) have previously been published. Andrew and Farnell's theory (Mol. Phys. 15, 157 (1968)) for the effects of Janti on NMR spectra has been extended to powdered samples, and methods for analyzing the resultant line shapes have been determined. Finally, the first reported experimental attempts to measure Janti are presented, and experimental proof that no elements of Janti(119Sn,119Sn) in hexa(p-tolyl)ditin are larger than 2900 Hz is given.
Language
English
Rights
License granted by Kristopher Harris (kjharris@ualberta.ca) on 2009-06-05T22:49:47Z (GMT): Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of the above terms. The author reserves all other publication and other rights in association with the copyright in the thesis, and except as herein provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
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