Tris(2-pyridylthio)methane, [Tptm]H, has been employed to synthesize the mononuclear alkyl zinc hydride complex, [kappa(3)-Tptm]ZnH, which has been structurally characterized by X-ray diffraction. [kappa(3)-Tptm]ZnH provides access to a variety of other [Tptm]ZnX derivatives. For example, [kappa(3)-Tptm]ZnH reacts with (i) R3SiOH (R = Me, Ph) to give [kappa(3)-Tptm]ZnOSiR3, Me3SiX (X = Cl, Br, I) to give [kappa(4)-Tptm]ZnX, and (iii) CO2 to give the formate complex, [kappa(4)-Tptrri]ZnO2CH. The bis(trimethylsilyl)amide complex [kappa(3)-Tptm]ZnN(SiMe3)(2) also reacts with CO2, but the product obtained is the isocyanate complex, [kappa(4)-Tptm]ZnNCO. The formation of [kappa(4)-Tptm]ZnNCO is proposed to involve initial insertion of CO2 into the ZnN(SiMe3)(2) bond, followed by migration of a trimethylsilyl group from nitrogen to oxygen to generate [kappa(4)-Tptm]ZnOSiMe3 and Me3SiNCO, which subsequently undergo CO2-promoted metathesis to give [kappa(4)-Tptm]ZnNCO and (Me3SiO)(2)CO.