Synthesis and studies of late transition metal complexes and their reactions with small unsaturated molecules

Thomas Byron Peters, Purdue University

Abstract

Starting from the previously reported compound (Co$\sb2(\mu$-CO)(CO)$\sb2(\mu$-dppm)$\sb2(\mu$-I)) (I) (1), several novel cobalt compounds were prepared and characterized including (Co$\sb2(\mu$-CO)(CNMe)$\sb4(\mu$-dppm)$\sb2$) (PF$\sb6\rbrack\sb2$ (2), (Co$\sb2(\mu$-CNxylyl)(CNxylyl)$\sb2(\mu$-dppm)$\sb2 (\mu$-I)) (I) (3), (Co$\sb2(\mu$-CNBz)(CNBz)$\sb2(\mu$-dppm)$\sb2(\mu$-I)) (BPh$\sb4$) (4), (Co(CNxylyl)$\sb3$(dppm)) (PF$\sb6$) (5), and Co$\sb2(\mu$-CNxylyl)$\sb2$(CNxylyl)$\sb4(\mu$-dppm) (6). The reaction chemistry of these compounds was explored and patterns of reactivity were discovered. It was found that compound (5) could be reduced to compound (6), causing an interesting monomeric to dimeric structure change. The relatively new analysis technique, spectroelectrochemistry, was done of compounds (5) and (6). X-ray crystal structures of (2), (5), and (6) were also accomplished. The complex Ni(CNxylyl)4 (7) was prepared and characterized. Theoretical studies of (7) were done on the relationship between CNR isonitrile bending angles and backbonding. Compound (7) was also found to undergo a metathesis reaction with CO$\sb2$ in the presence of Li$\sp{+}$.

Degree

Ph.D.

Advisors

Kubiak, Purdue University.

Subject Area

Chemistry

COinS