Silylene-S-thione [PhC(NtBu)Si(═S)N(SiMe)] (2) and silylene-Se-selone [PhC(NtBu)Si(═Se)N(SiMe)] (3) compounds were prepared from the silylene [PhC(NtBu)SiN(SiMe)] (1) with 1 equiv of 1/8 S and 1 equiv of Se powder, respectively, in high yields. Furthermore, compounds 2 and 3 reacted with CuCl and CuBr and yielded [{PhC(NtBu)}Si(═S→CuX)N(SiMe)] (X = Cl (4), Br (5)) and [{PhC(NtBu)}Si(═Se→CuX)N(SiMe)] (X = Cl (6), Br (7)), respectively. Complexes 4-7 can also be obtained from the direct reaction of sulfur and selenium with the corresponding silylene copper complexes [{PhC(NtBu)}Si{N(SiMe)}]CuX (X = Cl (8), Br (9)). The latter route avoids the preparation of the highly reactive silylene chalcogenones. For comparison purposes the silylene PhC(NtBu)SiN(SiMe) in 2 and 3 was replaced by NHC (1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) (10). The resulting products NHC═S (thione 11) and NHC═Se (selenone 12) react with CuBr and lead to the expected complexes (NHC═S→CuBr) (13) and (NHC═Se→CuBr) (14). However, unlike silylene complexes, 13 and 14 cannot be prepared by reacting NHC-CuBr (15) with chalcogens.

N-Heterocyclic carbene, silylene and germylene ligand-based cationic Au(i)–arene complexes were prepared and employed as catalysts in the glycosidation reaction.

Realization of a hitherto elusive unsupported η6 binding mode of benzene to a copper(i) cation employing silylene as a ligand. The back-donation from Cu to Si(ii) diminishes the repulsion between d-electrons and the benzene ring and enforces the η6 binding mode.

A donor-stabilized silylene 4 featuring a Ni(0)-based donating ligand was synthesized. Complex 4 exhibits a pyramidalized and nucleophilic Si(II) center and shows a peculiar behavior due to the cooperative reactivity of Si and Ni centers. Calculations indicate that the orientation of Ni-ligands with respect to the silylene moiety is crucial in determining the role of Ni-fragment (Lewis acid or Lewis base) towards silylene. Indeed, a simple 90° rotatation of Si-Ni-bond, reverses the role of Ni, and transforms a classical silylene→Ni(0) complex into an unprecedented Ni(0)→silylene complex.