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PO → Si intramolecular coordination in the derivatives of 1,4‐phosphasilacyclohexane 1‐oxides
Author(s) -
Shainyan Bagrat A.,
Lazareva Natalia F.
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21788
Subject(s) - intramolecular force , conformational isomerism , natural bond orbital , chemistry , silicon , atom (system on chip) , ring (chemistry) , crystallography , solvent , computational chemistry , polar , stereochemistry , density functional theory , molecule , organic chemistry , computer science , physics , astronomy , embedded system
The chair and boat conformers for a series of derivatives of 1,4‐phosphasilacyclohexane 1‐oxides have been calculated at the B3LYP/6‐311+G** level of theory in the gas phase and taking into account the effect of solvent polarity using the IEF‐PCM model. The stability of the boat conformers containing pentacoordinate silicon due to formation of the PO→Si intramolecular coordination bond depends on the environment of the phosphorus atom and polarity of the solvent, and the strength of the transannular bond depends also on the nature of the substituents at the silicon atom. The highly polar boat conformers are strongly stabilized in the DMSO solution. NBO analysis showed the importance of the σ(CSi) → σ*(H 3 CN) hyperconjugative interaction in the two H 3 CNCSi fragments of the ring favoring the formation of the pentacoordinate silicon atom. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009