Date of Award
Doctor of Philosophy
John G. Verkade
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.
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Colleen Margaret Duff
Duff, Colleen Margaret, "Synthesis of a new tetradentate phosphine and its coordination chemistry with group 10 metals " (1987). Retrospective Theses and Dissertations. 8635.