122114-74-3Relevant academic research and scientific papers
Scope and mechanism of oxidative addition of C=S bonds to trinuclear platinum and palladium complexes
Bradford, Arleen M.,Jennings, Michael C.,Puddephatt, Richard J.
, p. 2367 - 2371 (2008/10/08)
The coordinatively unsaturated complex [Pt3(μ3-CO)(μ-dppm)3]2+ (dppm = Ph2PCH2PPh2) reacts with the heterocumulenes S=C=E, where E = N-, O, S, or NR, to give the corresponding adducts [Pt3(S= C=E)(μ3-CO)(μ-dppm)3]2+, followed by oxidative addition of the C=S bond and loss of CO to give the products [Pt3(μ3-S)(C≡E)(μ-dppm)3] 2+. These products were characterized by elemental analysis and multinuclear NMR spectroscopy. A further intermediate, identified by 31P and 13C NMR as [Pt3(μ3-S)(CO)(μ-dppm)3]2+, was formed in the cases where E = O or NR but not when E = S or N-. The complex [Pd3(μ3-CO)(μ-dppm)3]2+ reacts with CS2 to give a complex that was tentatively identified as [Pd3(μ-CS2)(μ-dppm)3]2+. In these reactions, the nuclearity of the complexes is maintained by the bridging dppm ligands, and this leads to important differences from related chemistry of other Pt3 and Pd3 clusters. The reaction of [M3(SCN)(μ-CO)(μ-dppm)3]2+ to give [M3(μ3-S)(CN)(μ-dppm)3]+ and CO is retarded by free CO, under conditions of either thermal (M = Pd) or photochemical (M = Pt) activation, and the thermal reaction of [Pt3(μ3-CO)(μ-dppm)3]2+ with CS2 is also retarded by free CO. Two different mechanisms of reaction are throught to operate, and these are discussed.
