作者:Samuel J. Mitton、Robert McDonald、Laura Turculet
DOI:10.1016/j.poly.2012.07.072
日期:2013.3
The compound (2-Cy2PC6H4)(2)SiMe2 (1) reacted readily with Pt(PPh3)(4) to undergo Si-C(sp(3)) bond cleavage and form the Pt-II species (Cy-PSiP)PtMe (2, Cy-PSiP = kappa(3)-(2-Cy2PC6H4)(2)SiMe-). The silane 1 also undergoes Si-C(sp(3)) bond activation with the Pt-II precursor [(Me2S)PtMe2](2) to generate 2. Two intermediate species were observed in situ during the reaction of I with [(Me2S)PtMe2](2). One intermediate was tentatively assigned as the bis(phosphino) Pt-II species (kappa(2)-Cy-PSiP)PtMe2 (4), which was crystallographically characterized. A second intermediate (5) was tentatively assigned as the Pt-IV species (Cy-PSiP)PtMe3 resulting from Si-C(sp(3)) bond cleavage in 4. In an effort to prepare a (Cy-PSiP)Pt-IV species that may serve as a model for 5, complex 2 was reacted with MeI and 12, respectively; both reactions resulted in the quantitative formation of (Cy-PSiP)PtI (6), which could also be independently prepared by the reaction of (COD)PtI2 with (Cy-PSiP)H. The reaction of (Cy-PSiP)H with PtMe3I resulted in the formation of a Pt-IV species (7) as the major product. Complex 7 was tentatively assigned as (Cy-PSiP)PtMe2I, and undergoes relatively facile elimination of ethane to form 6. (C) 2012 Elsevier Ltd. All rights reserved.