TY - JOUR
T1 - Synthesis of [Pt(SnBut3)(IBut)(μ-H)]2, a Coordinatively Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt-Sn Complexes
AU - Koppaka, Anjaneyulu
AU - Yempally, Veeranna
AU - Zhu, Lei
AU - Fortman, George C.
AU - Temprado, Manuel
AU - Hoff, Carl D.
AU - Captain, Burjor
N1 - Funding Information:
The National Science Foundation (CHE-1300206) and the Spanish Ministry of Economy and Competitiveness CTQ2012-36966) are gratefully acknowledged for support of this work.
PY - 2016/1/4
Y1 - 2016/1/4
N2 - The reaction of Pt(COD)2 with one equivalent of tri-tert-butylstannane, But3SnH, at room temperature yields Pt(SnBut3)(COD)(H)(3) in quantitative yield. In the presence of excess But3SnH, the reaction goes further, yielding the dinuclear bridging stannylene complex [Pt(SnBut3)(μ-SnBut2)(H)2]2 (4). The dinuclear complex 4 reacts rapidly and reversibly with CO to furnish [Pt(SnBut3)(μ-SnBut2)(CO)(H)2]2 (5). Complex 3 reacts with N,N′-di-tert-butylimidazol-2-ylidene, IBut, at room temperature to give the dinuclear bridging hydride complex [Pt(SnBut3)(IBut)(μ-H)]2 (6). Complex 6 reacts with CO, C2H4, and H2 to give the corresponding mononuclear Pt complexes Pt(SnBut3)(IBut)(CO)(H)(7), Pt(SnBut3)(IBut)(C2H4)(H)(8), and Pt(SnBut3)(IBut)(H)3 (9), respectively. The reaction of IBut with the complex Pt(SnBut3)2(CO)2 (10) yielded an abnormal Pt-carbene complex Pt(SnBut3)2(aIBut)(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(SnBut3)(IBut)(H)3 have been performed, for NHC = IMe and R = Me and for NHC = IBut and R = But. The structures of complexes 3-8 and 11 have been determined by X-ray crystallography and are reported.
AB - The reaction of Pt(COD)2 with one equivalent of tri-tert-butylstannane, But3SnH, at room temperature yields Pt(SnBut3)(COD)(H)(3) in quantitative yield. In the presence of excess But3SnH, the reaction goes further, yielding the dinuclear bridging stannylene complex [Pt(SnBut3)(μ-SnBut2)(H)2]2 (4). The dinuclear complex 4 reacts rapidly and reversibly with CO to furnish [Pt(SnBut3)(μ-SnBut2)(CO)(H)2]2 (5). Complex 3 reacts with N,N′-di-tert-butylimidazol-2-ylidene, IBut, at room temperature to give the dinuclear bridging hydride complex [Pt(SnBut3)(IBut)(μ-H)]2 (6). Complex 6 reacts with CO, C2H4, and H2 to give the corresponding mononuclear Pt complexes Pt(SnBut3)(IBut)(CO)(H)(7), Pt(SnBut3)(IBut)(C2H4)(H)(8), and Pt(SnBut3)(IBut)(H)3 (9), respectively. The reaction of IBut with the complex Pt(SnBut3)2(CO)2 (10) yielded an abnormal Pt-carbene complex Pt(SnBut3)2(aIBut)(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(SnBut3)(IBut)(H)3 have been performed, for NHC = IMe and R = Me and for NHC = IBut and R = But. The structures of complexes 3-8 and 11 have been determined by X-ray crystallography and are reported.
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U2 - 10.1021/acs.inorgchem.5b02441
DO - 10.1021/acs.inorgchem.5b02441
M3 - Article
AN - SCOPUS:84953439769
VL - 55
SP - 307
EP - 321
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 1
ER -