PSiP group 11 metal

Silyl PSiP ligands were first reported by Stobart and coworkers [35, 36] in the 1980s, who prepared a series of platinum group metal complexes supported... 

The published chemistry of group 8 metal PSiP complexes is thus far restricted to the synthesis of Ru" complexes. PSiP complexes of Ru" were first reported by Stobart and coworkers, who studied the complexation of the bis(phosphinoalkyl) silanes 1 and 5 with Ru carbonyl species. In an initial study, low yields of the 18-electron hydrido carbonyl complexes [K -(Ph2P(CH2)n)2SiMe]Ru(H)(CO)2 (17, n = 2 18, =3) were obtained upon reaction of either 1 or 5 with RUjICOljj (Scheme 6.5) [36]. Complex 18 was crystallographically characterized and featured... 

Our group has explored in detail the reactivity of 82 and the dicyclohexylphos-phino analog 84 (Scheme 6.19). These Pt chloride complexes were utiHzed as precursors for the synthesis of Pt alkyl complexes and cations of the type [(PSiP)Pt]", with the goal of accessing highly reactive metal complexes that would engage in E-H bond activation chemistry [77]. Indeed, square planar Pt alkyl and aryl complexes of the type (R -PSiP)PtR (85, R = Ph, R = CH2Ph 86,... 

Scheme 6.19 Synthesis of group 10 metal PSiP complexes.

Milstein and coworkers [43] have also contributed to group 10 metal PSiP chemistry, having attempted to stabilize Pt silanone (R2Si=0) species in the framework of a PSiP pincer. The attempted deprotonation of the silanol Pt" complex 120 with a strong base resulted in an unusual rearrangement process that afforded the dinuclear Pt hydride complex 125 (Scheme 6.26). A proposed... 

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