Bond Characterization of a Unique Thiathiophthene Derivative: Combined Charge Density Study and X-ray Absorption Spectroscopy

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• 作者：Yu-Chun Chuang ; Ya-Wen Li ; I-Jui Hsu ; Gene-Hsiang Lee ; Yu Wang
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：October 7, 2013
• 年：2013
• 卷：52
• 期：19
• 页码：10958-10967
• 全文大小：675K
• 年卷期：v.52,no.19(October 7, 2013)
• ISSN：1520-510X

文摘

Thiathiophthene (TTP), a planar molecule with two fused heterocyclic five-membered rings and an essentially linear S鈥揝鈥揝 bond, is a molecule of great interest due to its unique chemical bondings. To elucidate the remarkable bonding nature, a combined experimental and theoretical study on the electron density distribution of 2,5-dimethyl-3,4-trimethylene-6a-TTP (1) is investigated based on a multipole model through high-resolution X-ray diffraction data experimentally and on the density functional calculations (DFT) theoretically. In addition, S K-edge X-ray absorption spectroscopy (XAS) is measured to verify the chemical bonding concerning the sulfur atoms. The molecule can be firmly described as 10蟺 electron with aromatic character among the eight atoms, S₃C₅, of the two fused five-membered rings plus three-center four-electron 蟽 character along the S鈥揝鈥揝 bond. Such bonding description is verified with the calculated XAS spectrum, where the pre-edge absorption for transitions from S 1s to 蟺* and 蟽* are located. The three-center four-electron S鈥揝鈥揝 蟽 bond makes the terminal S atoms richer in electron density than the central one.