Studies of the reactions of platinum halo complexes with tin(II) halides

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

“…The following reagents were used as supplied: dppf (Aldrich), dppm (Merck), dppe (Merck), dppp (Merck), dppb (Acros), and dpppe (Alfa Aesar). 31 2 ] and cis-[PtCl 2 (P 2 )] (P ¼ Ph 3 P and (MeO) 3 P; P 2 ¼ dppm (see 9), dppe (see 11), and dpppe (see 4)) were prepared as described in [2] [35], and cis-[PtBr 2 (Ph 3 P) 2 ] (c-23) [24] were prepared in good yield by metathesis of cis-[PtCl 2 (P 2 )] with two equiv. of KX (X ¼ Br, I) in acetone.…”

“…Three reaction types, i.e., simple insertion of SnCl 2 into the PtÀCl bond, ligand migration, and/or ligand rearrangement with the displacement of ligand, have been observed in different solvents [6]. For example, the reaction of complex [PtCl(P)(P 2 The coupling constant 1 J(Pt,P) is one of the best tools for the characterization of the Pt complexes containing phosphine ligands, because it is a sensitive function of the type of phosphine ligand and of the trans effect. Therefore, the reactions of a related series of dihaloplatinum(II) complexes containing phosphine ligands with SnX 2 (X ¼ Cl, Br, or I) are investigated in this work.…”

“…Other Pt/Sn mol ratios than 1 : 5 did not give rise to new compounds. We have recently reported that the reaction of cis-[PtCl 2 (P 2 )] 9 (P 2 ¼ dppm), 10 (P 2 ¼ dppa ¼ bis(diphenylphosphino)amine ¼ N-(diphenylphosphino)-P,P-diphenylphosphinous amide), and 11 (P 2 ¼ dppe) with SnCl 2 results in the insertion of SnCl 2 into both PtÀCl bonds to afford cis-[Pt(SnCl 3 ) 2 (P 2 )] [2]. It can be seen that the preferred ring sizes for the formation of cis-[Pt(SnCl 3 ) 2 (P 2 )] are 4-and 5-membered chelate rings, and cis-[PtCl(SnCl 3 )(P 2 )] is preferred for 6-, 7-, and 8-membered chelate rings.…”

“…These heterobimetallic complexes are widely applied as the useful homogeneous catalysts for the hydroformylation and hydrogenation of unsaturated hydrocarbons [5 -7]. The facile insertion of SnCl 2 into the PtÀCl bond and the stability of the trichlorostannyl complexes of Pt make them attractive as the catalyst precursor, however, the cocatalyst role of SnCl 2 is not yet fully understood [1] [8]. SnCl 2 can act as a Lewis acid, as the counter ion of SnCl À 3 , and as a ligand bonded to Pt [8].…”