Low-coordinate germylene and stannylene heterocycles featuring sterically tunable bis(amido)silyl ligands
A series of monomeric heterocyclic metallylenes [{iPr 2Si(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 (SiPh 3) 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.
Al-Rafia, S. M. Ibrahim,Lummis, Paul A.,Ferguson, Michael J.,McDonald, Robert,Rivard, Eric
experimental part
p. 9709 - 9717
(2011/01/12)
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