%0 Journal Article %A M. Ibrahim Al-Rafia, S. %A Lummis, Paul A. %A Ferguson, Michael J. %A McDonald, Robert %A Rivard, Eric %D 2010 %T Low-Coordinate Germylene and Stannylene Heterocycles featuring Sterically Tunable Bis(amido)silyl Ligands %U https://acs.figshare.com/articles/journal_contribution/Low_Coordinate_Germylene_and_Stannylene_Heterocycles_featuring_Sterically_Tunable_Bis_amido_silyl_Ligands/2721085 %R 10.1021/ic101485a.s002 %2 https://acs.figshare.com/ndownloader/files/4397038 %K iPr %K 2C %K 2Si %K group 14 centers %K chalcogen sources %K sulfido complexes %K steric protection %K dimeric oxo %K SiPh %K Structural analyses %K S 8 %K 3NO %K Stannylene Heterocycles %K metallylene %K steric bulk %K Dipp group %K NSiN chelate %X A series of monomeric heterocyclic metallylenes [{iPr2Si(NR)2}M:] (M = Ge and Sn; R = Dipp = 2,6-iPr2C6H3 or SiPh3) have been prepared. Preliminary atom-transfer chemistry involving the new low-valent germylenes with the chalcogen sources Me3NO and S8 yielded the corresponding dimeric oxo- and sulfido complexes (e.g., [{iPr2Si(NDipp)2}Ge(μ-E)]2; E = O and S). Structural analyses of the metallylenes and their oxidized products reveal that incorporation of the umbrella-shaped triarylsilyl groups (SiPh3) within the NSiN chelate confers additional steric protection about the group 14 centers relative to a Dipp group. The inclusion of sterically modifiable −SiAr3 (Ar = aryl) units as part of a bis(amido) ligand array represents a new approach in this field and holds considerable promise with regard to attaining increasingly higher degrees of steric bulk. %I ACS Publications