Inorganic Chemistry, Vol.55, No.1, 307-321, 2016
Synthesis of [Pt(SnBu3t)(IBut)(mu-H)](2), a Coordinative ly Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt-Sn Complexes
The reaction of Pt(COD)(2) with one equivalent of tri-tert-butylstannane, But,SnH, at room temperature yields Pt(SnBu3t)(COD)(H)(3) in quantitative yield. In the presence of excess (Bu3SnH)-Sn-t, the reaction goes further, yielding the dinudear bridging stannylene complex [Pt(SnBu3t)(mu-SnBu2t)(H)(2)](2) (4). The dinudear complex 4 reacts rapidly and reversibly with CO to furnish [Pt(SnBu3t)(mu-SnBu2t)(CO)(H)(2)](2) (5). Complex 3 reacts with N,N'-di-tert-butylimidazol-2-ylidene, IBut, at room temperature to give the dinudear bridging hydride complex [Pt(SnBu3t)(IBut)(mu-H)](2) (6). Complex 6 reacts with CO, C2H4, and H-2 to give the corresponding mononuclear Pt complexes Pt(SnBu3t)(IBut)(CO)(H)(7), Pt(SnBu3t)(IBut)(C2H4)(H)(8), and Pt(SnBu3t)(IBut)(H)(3) (9), respectively. The reaction of IBut with the complex Pt(SnBu3t)(2)(CO)(2) (10) yielded an abnormal Pt-carbene complex Pt(SnBu3t)(2)(aIBu(t))(CO) (11). DFT computational studies of the dimeric complexes [Pt(SnR3)(NHC)(mu-H)](2), the potentially more reactive monomeric complexes Pt(SnR3)(NHC)(H) and the trihydride species Pt(SnBu3t)(IBut)(H)(3) have been performed, for NHC = IMe and R = Me and for NHC = IBut and R = Bu-t. The structures of complexes 3-8 and 11 have been determined by X-ray crystallography and are reported.