Trisilaallene and the Relative Stability of Si3H4 Isomers.

Abstract

A theoretical quantum-mechanical study of trisilaallene, H2Si [Formula: see text] Si [Formula: see text] SiH2, and of 15 other Si3H4 isomers was carried out using ab initio and DFT methods with a variety of basis sets. Values given below are at B3LYP/6-31G(d,p). Unlike H2C [Formula: see text] C [Formula: see text] CH2 which is linear, H2Si [Formula: see text] Si [Formula: see text] SiH2 is highly bent at the central silicon atom, with a SiSiSi bending angle of 69.4°. The Si [Formula: see text] Si bond length is 2.269 Å, longer than a regular Si [Formula: see text] Si double bond (2.179 Å) but shorter than a Si-Si single bond (2.351 Å). The distance between the terminal silicon atoms is 2.583 Å, significantly longer than a Si-Si single bond. The geometry and electronic properties of H2Si [Formula: see text] Si [Formula: see text] SiH2 are similar to those of the corresponding trisilacyclopropylidene, which is only 2.7 kcal/mol higher in energy. A barrier of only 0.1 kcal/mol separates trisilacyclopropylidene and trisilaallene which can be described as bond-stretch isomers. Sixteen minima were located on the Si3H4 PES, most of them within a narrow energy range of ca. 10 kcal/mol. Six of the Si3H4 isomers are analogous to the classic C3H4 minima structures; however, the other Si3H4 isomers do not have carbon analogues, and they are characterized by hydrogen-bridged structures.