Department of Chemistry, Columbia University, New York, New York 10027, USA.
J Am Chem Soc. 2011 Jun 29;133(25):9708-11. doi: 10.1021/ja2035706. Epub 2011 Jun 6.
Tris(2-pyridylthio)methane, [Tptm]H, has been employed to synthesize the mononuclear alkyl zinc hydride complex, [κ(3)-Tptm]ZnH, which has been structurally characterized by X-ray diffraction. [κ(3)-Tptm]ZnH provides access to a variety of other [Tptm]ZnX derivatives. For example, [κ(3)-Tptm]ZnH reacts with (i) R(3)SiOH (R = Me, Ph) to give [κ(4)-Tptm]ZnOSiR(3), (ii) Me(3)SiX (X = Cl, Br, I) to give [κ(4)-Tptm]ZnX, and (iii) CO(2) to give the formate complex, [κ(4)-Tptm]ZnO(2)CH. The bis(trimethylsilyl)amide complex [κ(3)-Tptm]ZnN(SiMe(3))(2) also reacts with CO(2), but the product obtained is the isocyanate complex, [κ(4)-Tptm]ZnNCO. The formation of [κ(4)-Tptm]ZnNCO is proposed to involve initial insertion of CO(2) into the Zn-N(SiMe(3))(2) bond, followed by migration of a trimethylsilyl group from nitrogen to oxygen to generate [κ(4)-Tptm]ZnOSiMe(3) and Me(3)SiNCO, which subsequently undergo CO(2)-promoted metathesis to give [κ(4)-Tptm]ZnNCO and (Me(3)SiO)(2)CO.
三（2-吡啶基硫代）甲烷，[Tptm]H，已被用于合成单核烷基锌氢化物配合物，[κ(3)-Tptm]ZnH，其结构已通过 X 射线衍射进行了表征。[κ(3)-Tptm]ZnH 可以得到各种其他[Tptm]ZnX 衍生物。例如，[κ(3)-Tptm]ZnH 与（i）R(3)SiOH（R = Me，Ph）反应得到[κ(4)-Tptm]ZnOSiR(3)，（ii）Me(3)SiX（X = Cl，Br，I）反应得到[κ(4)-Tptm]ZnX，（iii）CO(2)反应得到甲酸盐配合物，[κ(4)-Tptm]ZnO(2)CH。双（三甲基硅基）酰胺配合物[κ(3)-Tptm]ZnN(SiMe(3))(2)也与 CO(2)反应，但得到的产物是异氰酸酯配合物，[κ(4)-Tptm]ZnNCO。[κ(4)-Tptm]ZnNCO 的形成被提出涉及 CO(2)对 Zn-N(SiMe(3))(2)键的初始插入，随后氮上的一个三甲基硅基从氮迁移到氧生成[κ(4)-Tptm]ZnOSiMe(3)和 Me(3)SiNCO，它们随后在 CO(2)促进的复分解作用下生成[κ(4)-Tptm]ZnNCO 和(Me(3)SiO)(2)CO。
