A Theoretical and Structural Investigation of Thiocarbon Anions
Chen Z, Sutton L, Moran DM, Hirsch A, Thiel W, Schleyer P (2003)
Publication Type: Journal article, Original article
Publication year: 2003
Journal
Original Authors: Chen Z., Sutton L.R., Moran D., Hirsch A., Thiel W., Von Rague Schleyer P.
Publisher: American Chemical Society
Book Volume: 68
Pages Range: 8808-8814
Journal Issue: 23
DOI: 10.1021/jo035144l
Abstract
Density functional theory energies, geometries, and population analyses as well as nucleus-independent chemical shifts (NICS) have been used to investigate the structural and magnetic evidence for cyclic CS - and CS (n = 3-6) electron delocalization. Localized molecular orbital contributions to NICS, computed by the individual gauge for localized orbitals method, dissect π effects from the σ single bonds and lone pair influences. CS (n = 3-5) structures in D symmetry are minima. Their aromaticity decreases with increasing ring size. C S is both σ and π aromatic, while CS and CS are much less aromatic. NICS(0)π, the C-C(π) contribution to NICS(0) (i.e., at the ring center), decreases gradually with ring size. In contrast, cyclic CS prefers D symmetry due to the balance between aromaticity, strain energy, and the S-S bond energies and is as aromatic as benzene. The theoretical prediction that CS has D minima was confirmed by X-ray structure analysis. Comparisons between thiocarbons and oxocarbons based on dissected NICS analysis show that CS (n = 3-5) and CS are less aromatic in D symmetry than their oxocarbon analogues.
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APA:
Chen, Z., Sutton, L., Moran, D.M., Hirsch, A., Thiel, W., & Schleyer, P. (2003). A Theoretical and Structural Investigation of Thiocarbon Anions. Journal of Organic Chemistry, 68(23), 8808-8814. https://dx.doi.org/10.1021/jo035144l
MLA:
Chen, Zhongfang, et al. "A Theoretical and Structural Investigation of Thiocarbon Anions." Journal of Organic Chemistry 68.23 (2003): 8808-8814.
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