Synthesis, characterization, and electrochemical studies on some selected dinuclear rhodium complexes

Author

Christopher James Janke

Date of Award

3-1986

Degree Type

Thesis

Degree Name

Master of Science

Major

Chemistry

Major Professor

Clifton Woods

Committee Members

William Bull, James Chambers

Abstract

New binuclear rhodium(I) complexes containing terminal carbon monoxide, bridging dpm (bis(diphenylphosphino)methane) ligands, and a triazolate anion or pyrazolate (pz) derivative in the bridgehead position have been investigated. Products obtained by the chemical oxidation of these complexes using I₂, Br₂, and CI₂ have also been synthesized. It has been found that with some of the pz derivatives that are not substituted in the 4-position treatment of Br₂ and CI₂ with some of the complexes leads to substitution in the 4-position as well as oxidative addition at the metal centers.

The electrochemical behavior of several rhodium complexes has been examined using cyclic voltammetry and bulk electrolysis. A new Rh(II)-Rh(II) complex has been prepared by the electrochemical oxidation of a methylene chloride solution containing trans-Rh₂CI₂(μ-C0)(μ-Cl)(dpm)₂ in the presence of excess chloride to give the compound, [Rh₂CI₂(μ-C0)(μ-Cl)(dpm)₂]PF₆, 4. This new product when treated with CO undergoes simultaneous substitution, addition, and reduction reactions to produce a mixture of Rh(I)-Rh(I) and Rh(II)- Rh(II) dimers.

Recommended Citation

Janke, Christopher James, "Synthesis, characterization, and electrochemical studies on some selected dinuclear rhodium complexes. " Master's Thesis, University of Tennessee, 1986.
https://trace.tennessee.edu/utk_gradthes/13725