Date of Award

1988

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Leslie G. Butler

Abstract

Solid-state deuterium NMR spectroscopic techniques have been applied to a series of organic and organometallic systems. The construction and operation of an ADLF (adiabatic demagnetization in the laboratory frame) spectrometer is described in detail. The instrument has been used to obtain high-field solid-state deuterium NMR spectra for a series of para-substituted phenyl acetic acids which have been deuteriated at the methylene site, as well as $d\sb1$-napthalene, triphenylphosphonium-(methyl-$d\sb3$) bromide, and barium chlorate monohydrate (25% deuteriated). The data for the para-substituted phenyl acetic acids show that the two methylene deuterons are inequivalent. This inequivalency is due to the difference in the $\sp2$H-C$\sb1$-C$\sb2$-O torsion angle for the deuterium sites; here C$\sb1$ refers to the methylene carbon, C$\sb2$ refers to the carboxylic acid carbon, and O refers to the hydroxyl oxygen. In addition, static values of the deuterium quadrupolar coupling constant and asymmetry parameter have been obtained for (C$\sp2$H$\sb3$)(C$\sb6$H$\sb5$)$\sb3$PBr and Ba(ClO$\sb3$)${\cdot}\sp1$H$\sp2$HO, two systems where motional averaging of these two parameter have been previously observed. Conventional high-field solid-state deuterium NMR spectroscopy has been applied to three organometallic hydride systems. The spectrum of (($\eta\sp5$-C$\sb5$H$\sb5$)$\sb2$Zr($\sp2$H)$\sb2$) $\sb{\rm x}$ is reported; both the terminal and bridging site are observed and have been identified. Variable temperature solid-state deuterium NMR spectra have been acquired for (PPN) $\sp+$ ($\sp2$HFe(CO)$\sb4$) $\sp-$. The data have been analyzed by lineshape simulations and interpreted in terms of a libration of the Fe-$\sp2$H bond about the C$\sb3$ molecular axis of the anion. From an Arrhenius plot, the activation energy of the process is calculated to be 18(2) kJoules/mole. Preliminary results of a solid-state deuterium NMR spectroscopic study of two bridging chromium carbonyl complexes and one terminally bonded chromium carbonyl complex are also reported.

Pages

264

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