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 [N 3 C] coordination environment. Specifically, [Tptm]H reacts with Cd[N(SiMe 3 ) 2 ] 2 to afford [Tptm]CdN(SiMe 3 ) 2 , which thereby provides access to other derivatives. For example, [Tptm]CdN(SiMe 3 ) 2 reacts with (i) CO 2 to form {[Tptm]Cd(μ-NCO)} 2 and (ii) Me 3 SiOH and Ph 3 SiOH to form {[κ 3 -Tptm]Cd(μ-OSiMe 3 )} 2 and [Tptm]CdOSiPh 3 , respectively. The siloxide compound {[κ 3 -Tptm]Cd(μ-OSiMe 3 )} 2 reacts with Me 3 SiX (X = Cl, Br, O 2 CMe) to give [Tptm]CdX, while the reaction with PhSiH 3 in the presence of CO 2 generates the formate complex, [Tptm]CdO 2 CH, thereby providing evidence for the generation of a proposed cadmium hydride intermediate, {[Tptm]CdH}.