Synthesis, structure, and reactivity of a mononuclear organozinc hydride complex: facile insertion of CO2 into a Zn-H Bond and CO2-promoted displacement of siloxide ligands.
作者： Wesley Sattler , Gerard Parkin
DOI: 10.1021/JA2035706
关键词:
摘要: Tris(2-pyridylthio)methane, [Tptm]H, has been employed to synthesize the mononuclear alkyl zinc hydride complex, [κ(3)-Tptm]ZnH, which structurally characterized by X-ray diffraction. [κ(3)-Tptm]ZnH provides access a variety of other [Tptm]ZnX derivatives. For example, reacts with (i) R(3)SiOH (R = Me, Ph) give [κ(4)-Tptm]ZnOSiR(3), (ii) Me(3)SiX (X Cl, Br, I) [κ(4)-Tptm]ZnX, and (iii) CO(2) formate [κ(4)-Tptm]ZnO(2)CH. The bis(trimethylsilyl)amide complex [κ(3)-Tptm]ZnN(SiMe(3))(2) also CO(2), but product obtained is isocyanate [κ(4)-Tptm]ZnNCO. formation [κ(4)-Tptm]ZnNCO proposed involve initial insertion into Zn-N(SiMe(3))(2) bond, followed migration trimethylsilyl group from nitrogen oxygen generate [κ(4)-Tptm]ZnOSiMe(3) Me(3)SiNCO, subsequently undergo CO(2)-promoted metathesis (Me(3)SiO)(2)CO.
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