Zinc and Cadmium Complexes of Chelating N-Heterocyclic Silylene and Their Reactivity toward Elemental Chalcogens

The reactions of the pyridine-functionalized silylene L^NSi [L = PhC(NtBu)₂; N = 2-(methylamido)pyridine] with zinc and cadmium halides are described. These resulted in the formation of a series of zinc and cadmium silylene complexes: [L^NSi-ZnX₂] (X = Cl, Br, I) and [{L^NSi-CdI₂}₂], which is the first cadmium silylene compound. Subsequent reaction of these silylene complexes with elemental sulfur and selenium under mild conditions at room temperature afforded under activation of these elements the corresponding silanethione-stabilized zinc [(L^NSi═S)-ZnX₂] (X = Cl, I) and cadmium [(L^NSi═S)-CdI₂] complexes and the silaneselenone-stabilized zinc species [(L^NSi═Se)-ZnCl₂]. A selective insertion of the group 16 elements into the M-Si bond of the silylenes was observed. Because of metal coordination, the Si-chalcogen bond lengths in the silanethiones and silaneselenones are enlarged and thus range between a single and a double bond. All new compounds were fully characterized by single-crystal X-ray diffraction analyses, multinuclear NMR spectroscopy, elemental analyses, and IR spectroscopy.