Hydride Migration from Silicon to an Adjacent Unsaturated Imino Carbon: Intramolecular Hydrosilylation

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)NNCR1R2; 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.