Date of Award
Doctor of Philosophy (PhD)
Irina P. Smoliakova
Cyclopalladated complexes (CPCs) possess a number of important properties and have been used in various application studies. However, preparation and uses of optically active CPCs with an (sp3)C–Pd bond have not been thoroughly investigated.
In this dissertation, the synthesis and applications of new enantiopure CPCs derived from naturally occurring and optically active D-camphor and L-fenchone are described. The preparation of these CPCs, which contain an (sp3)C–Pd bond, was accomplished by cyclopalladation of D-camphor O-methyloxime, L-fenchone O-methyloxime, L-fenchone oxime and camphor N,N-dimethylhydrazone using Pd(II) salts such as Pd(OAc)2 and Pd(MeCN)2Cl2.
Phosphination reactions of CPCs derived from D-camphor O-methyloxime and L-fenchone O-methyloxime, as well as other CN-, CS- and CP-dimeric CPCs having an (sp3)C–Pd bond, were investigated using KPPh2. These alternative CPCs were obtained from 8-methylquinoline, tri-(O-tolyl)phosphine, 2,6-dimethylthioanisole and trimesitylphosphine. In each case, when the CPC reacted with 4.5 equiv. of KPPh2, the corresponding NP-, SP- and PP-ligands were isolated in 13–51% yield. Reactions using only 1 equiv. of KPPh2 gave Âµ-chloro-Âµ-diphenylphosphido-CPCs as main products in 26–56% yield.
Proposed structures of new compounds obtained in the reactions were confirmed by spectroscopic methods and in some cases by X-ray crystallography. Purity and elemental composition of the synthesized complexes and organic compounds were confirmed by either satisfactory elemental analysis or high resolution mass spectra data.
Dickmu, Gerard Chepnda, "Synthesis And Applications Of Cyclopalladated Complexes Containing An (sp3)c‒pd Bond" (2015). Theses and Dissertations. 1889.