Cadmium Compounds with an [N3C] Atrane Motif: Evidence for the Generation of a Cadmium Hydride Species.

Tris(2-pyridylthio)methane ([Tptm]H) has been employed to synthesize a series of cadmium carbatrane compounds that feature an [N3C] coordination environment. Specifically, [Tptm]H reacts with Cd[N(SiMe3)2]2 to afford [Tptm]CdN(SiMe3)2, which thereby provides access to other derivatives. For example, [Tptm]CdN(SiMe3)2 reacts with (i) CO2 to form {[Tptm]Cd(μ-NCO)}2 and (ii) Me3SiOH and Ph3SiOH to form {[κ3-Tptm]Cd(μ-OSiMe3)}2 and [Tptm]CdOSiPh3, respectively. The siloxide compound {[κ3-Tptm]Cd(μ-OSiMe3)}2 reacts with Me3SiX (X = Cl, Br, O2CMe) to give [Tptm]CdX, while the reaction with PhSiH3 in the presence of CO2 generates the formate complex, [Tptm]CdO2CH, thereby providing evidence for the generation of a proposed cadmium hydride intermediate, {[Tptm]CdH}.