Multiple Bonding of Low-valent Silicon and Germanium to Group 6 and 9 Metals

This work focuses on the development of chemistry of low-coordinate silicon and germanium complexes. Utilization of a novel stable amino(chloro)germylene afforded preparation of a number group 6 and 9 metallogermylens and metal germylidyne complexes, such as previously unknown triplet ground state cobalt germylidyne. Tungstenacyclobutadiene and tungstenagermanacyclobutadiene were obtained in reactions of tungstenogermylene and tungsten germylidyne complex with bis(dimethylamino)acetylene, respectively. Reactivity study of NHC-stabilized dichlorogermylene and -stannylene towards a tungsten metallate led to isolation of NHC-stabilized metallotetrylidynium cations and a cationic germylidyne complex. Carbene supported diiodosilylene was shown to be a valuable starting material in a novel method for the synthesis of 1H-siloles via [2+2+1] cycloaddition with bis(dialkylamino)acetylenes. Furthermore, an isolated NHC adduct of the iodosilyliumylidene cation SiI+ revealed upon spectroscopic investigation an unprecedented C-HSi anagostic interaction.