ChemInform Abstract: Chemical and Photochemical Approaches to Amino(aryl)silylenes.

Abstract

1994organo-silicon compounds, isocyclic C derivatives organo-silicon compounds, isocyclic C derivatives S 0064 -187Chemical and Photochemical Approaches to Amino(aryl)silylenes.-Two different methods to generate silylenes stabilized by o-aminoaryl groups are reported. The α-halodemetalation of dihalogeno( aminoaryl)silanes using Li metal or Li-naphthalene leads to the same product, i.e. a stabilized sila-ylide (hypercoordinated silylene). The intramolecular Lewis base stabilization is not sufficient to isolate a monomeric product. The silylenes, however, can be trapped with 2,3-dimethylbutadiene (II) (→ (III), (V), (IX)). An unexpected intramolecular rearrangement to silaacenaphthene (VII) is observed in the case of a six-membered ring aminoaryl-coordinated silylene obtained from (VI). Photolysis of the silane (VIII) produces also a sila-ylide which can be trapped with (II) to give (IX) or with Et3SiH. -(CORRIU, R.; LANNEAU, G.; PRIOU, C.; SOULAIROL, F.; AUNER, N.; PROBST, R.; CONLIN, R.; TAN, C.; J. Organomet. Chem. 466 (1994) 1-2, 55-68; Lab. Precurseurs Organomet. Mater., Univ. Sci. Tech. Languedoc, 34095 Montpellier, Fr.; EN)