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Date of Award
Doctor of Philosophy (Ph.D.)
Emerson G. Cobb
First Committee Member
Second Committee Member
Richard P. Dodge
Third Committee Member
Richard L. Barry
Fourth Committee Member
Charles A. Matuszak
Much of the fundamental work on complexation of cycloolefins by platinum metals has been laid down by several workers and ranges from complexes of butadiene those of cyclododecatriene. The work here was chiefly a continuation of research on cycloolefin complexes which appear in papers by Kuljian and Frye (30,31,44). Most of this work on the complexes of cyclic seven, eight, and twelve carbon ligands was repeated here to insure a more complete laboratory background and for verification of previously reported literature data on these compounds. These compounds were used a s basis for comparison to original compounds developed in the research.
More precisely, the major cycloolefins involved in the current research are 1,3- and 1,5-cyclooctadiene, although complexes with cyclooctatetriene ligands have been attempted. As has been shown by several workers (5,31,51,52), the 1,3-cyclooctadiene, when complexed with a platinum metal ion, rearranges to the 1,5-cyclooctadiene moiety.
With the idea of this rearrangement in mind, this research was continued with complexes using as a ligand, a substituted alkyl or phenyl group attached to the cyclooctadiene ring. The initial step in such a synthesis was the preparation of a substituted cyclooctadiene.This was accomplished by means of the Grignard reaction using a bromocyclooctadiene and alkyl- or phenyl-Grignard reagent. With the knowledge that rearrangement to the 1,5- position occurs with normally complexed cyclooctadiene, it was of interest to determine whether or not a substituted group on the ring would have (1) any inductive effect or (2) any steric effect on the speed of reaction or in double bond rearrangement.
Mccauley, Gerald Brady. (1967). Palladium And Platinum Complexes Of Substituted Cycloolefins. University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/2824
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