Silaphenolates and Silaphenylthiolates Two Unexplored Unsaturated Silicon Compound Classes Influenced by Aromaticity 英文参考文献.docVIP

Molecules 2012, 17, 369-389; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Silaphenolates and Silaphenylthiolates: Two Unexplored Unsaturated Silicon Compound Classes Influenced by Aromaticity Alvi Muhammad Rouf and Henrik Ottosson * Department of Biochemistry and Organic Chemistry, Uppsala University, Box 576, 751 23 Uppsala, Sweden; E-Mail: alvi.muhammadrouf@biorg.uu.se * Author to whom correspondence should be addressed; E-Mail: Henrik.Ottosson@biorg.uu.se; Tel.: +46-(0)-18-471-3809; Fax: +46-(0)-18-471-3818. Received: 30 November 2011; in revised form: 23 December 2011 / Accepted: 23 December 2011 / Published: 2 January 2012 Abstract: Monosilicon analogs of phenolates and phenylthiolates are studied by quantum chemical calculations. Three different silaphenolates and three different silaphenylthiolates are possible; the ortho-, meta-, and para-isomers. For the silaphenolates, the meta-isomer is the thermodynamically most stable, regardless if the substituent R at Si is H, t-Bu or SiMe3. However, with R = H and SiMe3 the energy differences between the three isomers are small, whereas with R = t-Bu the meta-isomer is ~5 kcal/mol more stable than the ortho-isomer. For the silaphenylthiolates the ortho-isomer is of lowest energy, although with R = H the ortho- and meta-isomers are isoenergetic. The calculated nucleus independent chemical shifts (NICS) indicate that the silaphenolates and silaphenylthiolates are influenced by aromaticity, but they are less aromatic than the parent silabenzene. The geometries and charge distributions suggest that all silaphenolates and silaphenylthiolates to substantial degrees are described by resonance structures with an exocyclic C=O double bond and a silapentadienyl anionic segment. Indeed, they resemble the all-carbon phenolate and phenylthiolate. Silaphenylthiolates are less bond alternate and have