Conformational Transferability of the Sulfenyl Carbonyl Group 鈭扴C(O)鈥?in Cyclic Thioesters
详细信息 查看全文
- 作者：Nahir Y. Dugarte ; Mauricio F. Erben ; Evamarie Hey-Hawkins ; Peter L枚nnecke ; Sven Stadlbauer ; Mao-Fa Ge ; Yao Li ; Oscar E. Piro ; Gustavo A. Echeverr铆a ; Carlos O. Della V茅dova
- 刊名：The Journal of Physical Chemistry A
- 出版年：2013
- 出版时间：July 11, 2013
- 年：2013
- 卷：117
- 期：27
- 页码：5706-5714
- 全文大小：413K
- 年卷期：v.117,no.27(July 11, 2013)
- ISSN：1520-5215
文摘
The molecular and crystal structure of two dithiolactones (formally dimers of 蔚-caprothiolactone and 蠅-hexadecathiolactone) have been determined by X-ray diffraction at low temperature, revealing that the thioester group is planar with a synperiplanar orientation of the C鈺怬 double bond with respect to the S鈥擟 single bond. This conformational behavior is in contrast to that found for the smaller cyclic members of this family, where the antiperiplanar conformation is enforced. It is hypothesized that strain effects play a major role for the energy balance in the conformational preference. In this context, the molecular, vibrational (infrared and Raman), and electronic properties of 蔚-caprothiolactone have also been analyzed by using a combined experimental, including gas-phase helium I photoelectron spectroscopy, and computational approach.