Date of Award
Doctor of Philosophy
The first major part of this thesis involves the preparation and characterization of a new class of dinuclear platinum phosphine complexes with the ligand bis(dimethylphosphino)methane, dmpm.;The complex cis,cis- Pt(,2)Me(,4)((mu)-dmpm)(,2) proves to be very reactive towards oxidative additions, unlike the analogous complex cis,cis- Pt(,2)Me(,4)((mu)-dppm)(,2) ,dppm = Ph(,2)PCH(,2)PPh(,2). Thus the complex cis,cis- Pt(,2)Me(,4)((mu)-dmpm)(,2) reacts with halogens to give dmpm-bridged platinum (II)-platinum (IV) dimers, and with iodomethane to give a platinum (IV)-platinum (IV) dimer with bridging diphosphine ligands. Reactions of cis,cis- Pt(,2)Me(,4)((mu)-dmpm)(,2) with diiodoalkanes and with hydrogen chloride are also described.;The platinum (0) complexes Pt(,2)(PPh(,3))(,n)((mu)-dmpm)(,3) (n = 0, 1 or 2) have also been prepared and have been shown to be extremely reactive. A hydridoplatinum (II) complex Pt(,2)H(,2)((mu)-dmpm)(,3) PF(,6) (,2) is prepared from reaction of Pt(,2)(PPh(,3))((mu)-dmpm)(,3) and NH(,4)PF(,6). A platinum cluster complex has been isolated when Pt(,2)(PPh(,3))((mu)-dmpm)(,3) is subjected to Water Gas Shift Reaction conditions.;The differences in structures and reactivities of analogous dinuclear platinum complexes with bridging diphosphines R(,2)PCH(,2)PR(,2) can be explained in terms of the steric effects of the substituents R. Complexes with diphosphine ligands with R = Me, Et, ('i)Pr, Ph and also with the ligand ('t)BuHPCH(,2)PH('t)Bu, have been considered in this analysis of steric effects in dinuclear complexes.;The second major part of this thesis examines the decomposition of alkoxycyclopropanes catalyzed by Zeise's dimer Pt(,2)Cl(,2)((mu)-Cl)(,2)(C(,2)H(,4))(,2) . Three alkoxycyclopropanes, namely ethoxycyclopropane, n-butoxycyclopropane and 1-methy-1-methoxycyclopropane, have been studied. Mechanisms which can account for the products of catalyzed decomposition of these alkoxycyclopropanes have been proposed.;The rearrangement of platinacyclobutanes to give platinum-alkene complexes has also been studied. Deuterium-labelling experiments has been performed. From the structures of the products formed, it is clear that the rearrangement occurs via an (alpha)-elimination process, rather than the (beta)-elimination mechanism which had been claimed to occur by other research groups.
Ling, Samson See, "Dinuclear Platinum Phosphine Complexes And Platinacyclobutane Complexes" (1985). Digitized Theses. 1416.