AI Article Synopsis
- Thiathiophthene (TTP) is a unique molecule featuring two fused heterocyclic rings and a linear S-S-S bond, prompting interest in its chemical properties.
- A comprehensive study combining experimental high-resolution X-ray diffraction and theoretical density functional theory (DFT) explores the electron density distribution of a specific variant, 2,5-dimethyl-3,4-trimethylene-6a-TTP (1).
- The findings reveal that TTP exhibits aromatic character with a notable 10π electron configuration and a special three-center four-electron bond, leading to varying electron density among the sulfur atoms.
Article Abstract
Thiathiophthene (TTP), a planar molecule with two fused heterocyclic five-membered rings and an essentially linear S-S-S 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 10π electron with aromatic character among the eight atoms, S3C5, of the two fused five-membered rings plus three-center four-electron σ character along the S-S-S bond. Such bonding description is verified with the calculated XAS spectrum, where the pre-edge absorption for transitions from S 1s to π* and σ* are located. The three-center four-electron S-S-S σ bond makes the terminal S atoms richer in electron density than the central one.
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