Date of Award
Doctor of Philosophy
NiL(,4) complexes of various monocyclic and bicyclic phosphite ligands have been shown to be effective catalysts for the isomerization and hydrocyanation of olefins. The catalytic activity of the NiL(,4) complex was found to be dependent upon the electronic and structural properties of the phosphite ligand. It was observed that in order for these complexes to function as catalysts, the presence of either a protic or a Lewis acid co-catalyst was required.;An x-ray structural investigation of a NiL(,4) complex containing a monocyclic phosphite showed that the complex is tetrahedrally coordinated. It is suggested that the marked difference in catalytic activity of these complexes is derived from the differences in the steric properties of the ligands contained in the complex.;Attempts were also made at heterogenizing these homogeneous NiL(,4) catalysts by means of ligand exchange with nonchelating diphosphorus ligands (P-P). Complexes of the following types were prepared and (UNFORMATTED TABLE FOLLOWS); L L L;-Ni-(P-P)-Ni-(P-P)-Ni-; L L L(TABLE ENDS);evaluated as catalysts for olefin isomerization under the same conditions used with the homogeneous NiL(,4) catalysts.;The structural and electronic properties of some selected monocyclic aminophosphite compounds were investigated in order to determine how their unique electronic and structural properties could influence the catalytic activities of the NiL(,4) compounds they formed.;A method for the quantitative analysis of alcohols using phosphorus-containing derivatizing reagents was developed. This method entailed the use of quantitative ('31)P NMR techniques.
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David Evan Schiff
Schiff, David Evan, "Structural and electronic influences on phosphite basicity and its application to heterogeneous and homogeneous catalysis " (1983). Retrospective Theses and Dissertations. 8960.