Doctoral Dissertations

Date of Award

8-1984

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Clifton Woods

Committee Members

J.Q. Chambers, Gilbert Brown, Lew Keller

Abstract

Binuclear rhodium complexes containing isocyanide, carbon monoxide, halide, and the bridging ligands DPM, DAM, and DADPM (DPM = bis(diphenylphosphino)methane; DAM = bis(diphenylarsino)methane; DADPM = (diphenylarsino)(diphenylphosphino)methane) have been investigated. Some aspects of the photolytic and the electrochemical behavior of [Rh2(RNC)4(DPM)2]X2 (R = CH3, i-C3H7, nC4H9, t-C4H9; X = PF6-; BF4-) in coordinating and non-coordinating media are discussed. These compounds are capable of generating dihydrogen in aqueous acetone and are rapidly oxidized in solution in the presence of light at 520 nm. Electrochemical oxidation in the presence of coordinating species produces [Rh2(RNC)4Y2(DPM)2]X2 (Y = CN-, SCN-, I-, substituted pyridine). The structure and electrochemistry of Rh2(CO)2(DADPM)2 is also investigated. The reactivities and stabilities of Rh2(CO)2(DADPM)2 have also been investigated. The reactivities and stqabilities of Rh2(CO)2Cl2(DADPM)2 and its derivatives have been compared with the anlogous DPM and DAM compounds. The new DADPM complexes are characterized by infreared, ultraviolet-visible, and 31p and 13C NMR techniques.

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