Complexes of platinum containing sulphide and diphosphine ligands

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منو

" Complexes of platinum containing sulphide and diphosphine ligands "
N. Hadj-Bagheri R. J. Puddephatt

Document Type	:	Latin Dissertation
Language of Document	:	English
Record Number	:	1112716
Doc. No	:	TLpq303640164
Main Entry	:	N. Hadj-Bagheri
	:	R. J. Puddephatt
Title & Author	:	Complexes of platinum containing sulphide and diphosphine ligands\ N. Hadj-BagheriR. J. Puddephatt
College	:	The University of Western Ontario (Canada)
Date	:	1988
student score	:	1988
Degree	:	Ph.D.
Page No	:	1
Abstract	:	This thesis describes the chemistry of some homonuclear and mixed-metal complexes of platinum with sulphide and diphosphine ligands. (PtPh2(usd\eta\sp1usd-dmpm)2); dmpm = bis(dimethylphosphino)methane, is formed by the facile reaction of a diaryl platinum species with excess ligand. Synthesis of symmetric and asymmetric binuclear platinum complexes is achieved through the bonding of the uncoordinated phosphines to a second platinum centre. Oxidative addition reactions of these dimers are studied. (Pt2(mu-dppm)3); dppm = bis(diphenylphosphine)methane, reacts with carbonyl sulphide to yield (Pt2(mu-S)(mu-dppm)(usd\eta\sp1usd-dppm)2). This complex is used as a precursor in construction of trinuclear clusters. Coordination to a third centre can be achieved through the mono-coordinated diphosphine ligands as well as the mu-S bridge. The reaction of the dimer with d and d metal complexes yields (Pt2M(usd\mu\sb3usd-S)(mu-dppm)3) (X), (M = Pt, Pd, Rh, Ir, Cu, Ag, Au, Hg). The reactivity of these clusters is studied. (Pt2(mu-S)(mu-dppm)(usd\eta\sp1usd-dppm)2) reacts with dialkyl and diaryl platinum (II) complexes to give tetranuclear species. These are the first examples of tetraplatinum complexes containing quadruply bridging sulphide groups. The reactivity of (Pt2(mu-dppm)3) towards a variety of thiols is examined. Thiols oxidatively add to the dimer to give platinum (I) and platinum (II) complexes. Since platinum has a great affinity for sulphur, in some cases the dimer abstracts the sulphur atom from the thiol to form sulphur-bridged binuclear species. (Pt2(mu-dmpm)3(PPh3)) reacts with CO(g) under water-gas shift conditions to yield the stable 46-electron triplatinum cluster, (Pt3(mu-CO)(mu-dmpm)4) . The molecular structure of this cluster shows that the complex possesses strong Pt-Pt bonds. The cluster exhibits very little reactivity. The 46-electron count is not an unfavourable arrangement for low oxidation state platinum complexes since this cluster is clearly reluctant to add or lose a ligand to alter its electron count.
Subject	:	Chemistry
	:	Pure sciences