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

Abstract

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.