Low-Coordinate Germylene and Stannylene Heterocycles featuring Sterically Tunable Bis(amido)silyl Ligands

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• 作者：S. M. Ibrahim Al-Rafia ; Paul A. Lummis ; Michael J. Ferguson ; Robert McDonald ; Eric Rivard
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：October 18, 2010
• 年：2010
• 卷：49
• 期：20
• 页码：9709-9717
• 全文大小：1042K
• 年卷期：v.49,no.20(October 18, 2010)
• ISSN：1520-510X

文摘

A series of monomeric heterocyclic metallylenes [{<sup>isup>Pr<sub>2sub>Si(NR)<sub>2sub>}M:] (M = Ge and Sn; R = Dipp = 2,6-<sup>isup>Pr<sub>2sub>C<sub>6sub>H<sub>3sub> or SiPh<sub>3sub>) have been prepared. Preliminary atom-transfer chemistry involving the new low-valent germylenes with the chalcogen sources Me<sub>3sub>NO and S<sub>8sub> yielded the corresponding dimeric oxo- and sulfido complexes (e.g., [{<sup>isup>Pr<sub>2sub>Si(NDipp)<sub>2sub>}Ge(μ-E)]<sub>2sub>; E = O and S). Structural analyses of the metallylenes and their oxidized products reveal that incorporation of the umbrella-shaped triarylsilyl groups (SiPh<sub>3sub>) within the NSiN chelate confers additional steric protection about the group 14 centers relative to a Dipp group. The inclusion of sterically modifiable −SiAr<sub>3sub> (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.