Degree Type

Dissertation

Date of Award

1987

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

John G. Verkade

Abstract

Phosphines have been used extensively as ligands for transition metals. By altering the number and the spatial arrangement of the phosphorus atoms, one can significantly affect the character of the coordinated metal ion. A tetradentate phosphine (1) has been synthesized which is unique in its steric and geometric constraints.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) The carbon backbone of 1 obstructs octahedral coordination and should favor square planar and square pyramidal geometries for four and five coordinate complexes, respectively;The coordination chemistry of 1 has been investigated with Group 10 metals. Three modes of coordination have been observed for 1. The dinuclear complex (PdCl[subscript]2)[subscript]2(1), contains two six membered chelate rings and is formed by reaction of 1 and (PhCN)[subscript]2PdCl[subscript]2 in benzene. Further reaction of the dinuclear complex with 1 yields the mononuclear dication, ((solvent)Pd(1)) Cl[subscript]2. In the presence of water, and O[subscript]2, a dimethylsulfoxide solution of ((solvent)Pd(1)) Cl[subscript]2 reacts to form dimethylsulfone and a Pd product in which two arms of the phosphine remain coordinated, and two are oxidized and are dissociated. When chloride is replaced with a non-coordinating anion, dimethylsulfoxide is catalytically oxidized to dimethylsulfone;Attempts to prepare the analogous Ni(II) and Pt(II) complexes yielded fewer results. Formation of (Ni(1)) (ClO[subscript]4)[subscript]2 was achieved by the reaction of 1 with anhydrous Ni(ClO[subscript]4)[subscript]2. Reaction of 1 with Pt(II) salts and reagents generated insoluble polymers with the exception of CODPtI[subscript]2 which resulted in the reduction of Pt.

DOI

https://doi.org/10.31274/rtd-180813-11302

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/

Copyright Owner

Colleen Margaret Duff

Language

en

Proquest ID

AAI8805065

File Format

application/pdf

File Size

265 pages

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