title: Synthesis of [Pt(SnBu(t)3)(IBu(t))(μ-H)]2, a Coordinatively Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt-Sn Complexes.
abstract: The reaction of Pt(COD)2 with one equivalent of tri-tert-butylstannane, Bu(t)3SnH, at room temperature yields Pt(SnBu(t)3)(COD)(H)(3) in quantitative yield. In the presence of excess Bu(t)3SnH, the reaction goes further, yielding the dinuclear bridging stannylene complex [Pt(SnBu(t)3)(μ-SnBu(t)2)(H)2]2 (4). The dinuclear complex 4 reacts rapidly and reversibly with CO to furnish [Pt(SnBu(t)3)(μ-SnBu(t)2)(CO)(H)2]2 (5). Complex 3 reacts with N,N'-di-tert-butylimidazol-2-ylidene, IBu(t), at room temperature to give the dinuclear bridging hydride complex [Pt(SnBu(t)3)(IBu(t))(μ-H)]2 (6). Complex 6 reacts with CO, C2H4, and H2 to give the corresponding mononuclear Pt complexes Pt(SnBu(t)3)(IBu(t))(CO)(H)(7), Pt(SnBu(t)3)(IBu(t))(C2H4)(H)(8), and Pt(SnBu(t)3)(IBu(t))(H)3 (9), respectively. The reaction of IBu(t) with the complex Pt(SnBu(t)3)2(CO)2 (10) yielded an abnormal Pt-carbene complex Pt(SnBu(t)3)2(aIBu(t))(CO) (11). DFT computational studies of the dimeric complexes [Pt(SnR3)(NHC)(μ-H)]2, the potentially more reactive monomeric complexes Pt(SnR3)(NHC)(H) and the trihydride species Pt(SnBu(t)3)(IBu(t))(H)3 have been performed, for NHC = IMe and R = Me and for NHC = IBu(t) and R = Bu(t). The structures of complexes 3-8 and 11 have been determined by X-ray crystallography and are reported.
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33124, United States.
authors.forename: Anjaneyulu
authors.initials: A
authors.lastname: Koppaka
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33124, United States.
authors.forename: Veeranna
authors.initials: V
authors.lastname: Yempally
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33124, United States.
authors.forename: Lei
authors.initials: L
authors.lastname: Zhu
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33124, United States.
authors.forename: George C
authors.initials: GC
authors.lastname: Fortman
authors.affiliation: Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, Universidad de Alcalá , Madrid 28801, Spain.
authors.forename: Manuel
authors.initials: M
authors.lastname: Temprado
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33124, United States.
authors.forename: Carl D
authors.initials: CD
authors.lastname: Hoff
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33124, United States.
authors.forename: Burjor
authors.initials: B
authors.lastname: Captain