Synthesis of Novel Trialkyl(trichlorostannyl)platinum(IV) Complexes through SnCl2 Insertion into the Pt−Cl Bond

Reaction of SnCl2 with the trialkylplatinum(IV) complexes [PtClMe2(R)(bipy)] (1) resulted in the formation of the novel trialkyl(trichlorostannyl)platinum(IV) complexes [PtMe2(R)(SnCl3)(bipy)] (R = allyl (2a), Me (2b), Bz (2c)). The solid-state molecular structure of fac-[PtMe3(SnCl3)(bipy)] revealed a direct Pt−Sn bond (2.6497(2) Å) and three almost identical Pt−Me bond lengths (2.065(5) and 2.068(8) Å both cis and 2.069(5) Å trans to SnCl3). The presence of platinum satellites (1 J SnPt = 3267−4260 Hz) in the 119Sn NMR spectra of complexes 2 indicates that the direct platinum−tin bond is maintained in solution. Addition of 1 equiv of PPh3 to complexes 2 resulted in the formation of the trichlorostannate complexes fac-[PtMe2(R)(bipy)(PPh3)][SnCl3] (3). The absence of platinum satellites on the 119Sn NMR signal of 3 confirmed the ionic character of these complexes in solution.