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Why Is the Si-x sTretching Frequency of X8Si8O12 (X = H, Ch3, Cl) Much Higher Than That of XSi(OSiMe3)3?

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The totally symmetric stretching frequencies us(Si-X) of the octasilases-quioxanes X8Si8O,2 are distinctively larger than those of XSi(OSiMe3)3 for X = H, CH3, Cl whereas vs(Si-H) of H8Si8O12 and of H10Si10O15 differ very little. Inspection of the experimental data and molecular orbital calculations of the EHMO-ASED type show that this striking discrepancy is caused by the differences in the X-Si-O-Si conformations. The cage structure of X8Si8O12 requires the anti X-Si-O-Si conformation whereas the syn conformation is the stable one in XSi(OSiMe3)3. The Si-H bond order decreases from anti to syn caused by a decreasing interaction of the H-ls orbital with the Si-O-pπ type orbitals.

Affiliations: 1: Institute for Inorganic and Physical Chemistry, University of Berne, Freiestrasse 3, CH-3000 Bern 9, Switzerland


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