| Abstract
| - 1,3-Hydride shift from silicon to an adjacent imino carbon (“intramolecular hydrosilylation”) is observed in the reaction of MeSiHCl2 with O-trimethylsilyl-N-(alkylidenimino)imidates [RC(OSiMe3)NNCR1R2; R = Me, Ph, CH2Ph, t-Bu; R1, R2 = Me (1), (CH2)n (9), Ph, H (14)], leading to pentacoordinate silicon complexes. The reaction proceeds further to rearrange to the tricyclic pentacoordinate complexes, observed previously as products of intramolecular aldol condensation of imine moieties residing on two chelate rings in the reactions of XSiCl3 (X = alkyl, aryl) and 1.
- Reaction of MeSiHCl2 with O-trimethylsilylated hydrazide leads to a pentacoordinate silicon dichelate accompanied by 1,3-hydrogen shift from silicon to imino-carbon. The product reacts further to form a tricyclic rearrangement product, similar to intramolecular aldol condensation between imine groups on adjacent chelate rings in siliconium chlorides.
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