Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide

Abstract

AbstractReactions of SnCl2 with the complexes cis‐[PtCl2(P2)] (P2=dppf (1,1′‐bis(diphenylphosphino)ferrocene), dppp (1,3‐bis(diphenylphosphino)propane=1,1′‐(propane‐1,3‐diyl)bis[1,1‐diphenylphosphine]), dppb (1,4‐bis(diphenylphosphino)butane=1,1′‐(butane‐1,4‐diyl)bis[1,1‐diphenylphosphine]), and dpppe (1,5‐bis(diphenylphosphino)pentane=1,1′‐(pentane‐1,5‐diyl)bis[1,1‐diphenylphosphine])) resulted in the insertion of SnCl2 into the PtCl bond to afford the cis‐[PtCl(SnCl3)(P2)] complexes. However, the reaction of the complexes cis‐[PtCl2(P2)] (P2=dppf, dppm (bis(diphenylphosphino)methane=1,1′‐methylenebis[1,1‐diphenylphosphine]), dppe (1,2‐bis(diphenylphosphino)ethane=1,1′‐(ethane‐1,2‐diyl)bis[1,1‐diphenylphosphine]), dppp, dppb, and dpppe; P=Ph3P and (MeO)3P) with SnX2 (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX2(P2)]. In contrast, treatment of cis‐[PtBr2(dppm)] with SnBr2 resulted in the insertion of SnBr2 into the PtBr bond to form cis‐[Pt(SnBr3)2(dppm)], and this product was in equilibrium with the starting complex cis‐[PtBr2(dppm)]. Moreover, the reaction of cis‐[PtCl2(dppb)] with a mixture SnCl2/SnI2 in a 2 : 1 mol ratio resulted in the formation of cis‐[PtI2(dppb)] as a consequence of the selective halogen‐exchange reaction. 31P‐NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono‐ and bis(trichlorostannyl)platinum complexes. The effect of the alkane chain length of the ligand and SnII halide is described.