Journal of Physical Chemistry A, Vol.109, No.38, 8632-8636, 2005
Structure, strain, and degenerate rearrangement of tricyclo[2.1.0.0(1,3)]pentasilane and related molecules
We theoretically investigate a highly strained tricyclic silane (tricyclo[2.1.0.0(1,3)]pentasilane (4b), an isomer of pentasila[1.1.1]propellane (3b)) composed of three fused three-membered rings. The central ring is distorted. One of the fusion bonds in the central ring is shorter than the normal Si-Si single bond (2.350 angstrom) whereas the other is as long as the fusion bonds in bicyclo[1.1.0]tetrasilane (2b) (2.860 angstrom) and 3b (2.778 angstrom). The tricyclic silane is less strained than the carbon congener and more strained than the isomer 3b. The electron delocalization between one of the fusion bonds and the geminal Si-Si ring bonds elongates the fusion bond and stabilizes the molecules to reduce the strain. The silanes composed of the fused three-membered rings are less strained than the carbon congener. A degenerate rearrangement of a three-membered ring is predicted. The enthalpy of activation of the rearrangement of the distorted central ring is low (7.2kcal/mol) for 4b, but appreciable (22.3kcal/mol) for the germanium congener, tricyclo[2.1.0.0(1,3)]pentagermane (4c). We investigate the effects of the substituents on the distortion of the central three-membered ring and the degenerate rearrangement.