175404-80-5Relevant academic research and scientific papers
Cleavage of metal-carbon bonds in hydride-bridged platinum and palladium A-frame complexes
Zu, Chongfu,Anderson, Gordon K.
, p. 1760 - 1764 (2008/10/09)
The hydride-bridged A-frame complexes [RPt(μ-H)(μ -dppm)2PtR']PF6 and [RPt(μ-H)(μ-dppm)2 PdR']PF6 react with HCL (generated by reaction of acetyl chloride with water) in acetone-d6 solution by cleavage of one of the metal-carbon bonds. In the diplatinum systems the relative rates of Pt-C bond cleavage decrease in the order Me > ET > Ph, resulting in a single product in each case. For the heterometallic complexes reaction is faster at palladium, but mixtures of LBRPt(μ-H)(μ-dppm)2PdCl]PF6 and [ClPt(μ -H)(μ-dppm)2PdR']PF6 result in several instances. further reaction of these with HCL and/or CCl4 generates the chloride-bridged species [RPt(μ-Cl)(μ-dppm)2PdCl] PF6, formed, in some cases, by migration of the organic group from palladium to platinum. These complexes have been prepared also by reaction of [PtR(dppm-PP)(dppm-P)]PF6 with [PdCl2(cod)]. The [RPt(μ-Cl)(μ-dppm)2PdCl]PF6 complexes are fluxional at 298 K, although the motion may be arrested slightly below ambient temperature. A mechanism involving reversible bridge opening is proposed to account for the fluxional behavior.
