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Theoretical studies on the aromaticity of η-cyclopentadienyl cobalt dithiolene complexes |
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| Authors: | Yan-Hong Cui Wei Quan Tian Ji-Kang Feng Zi-Zhong Liu Wei-Qi Li |
| Affiliation: | aState Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China bCollege of Chemistry, Jilin University, Changchun 130023, China cCollege of Chemistry and Environment Science, Inner Mongolia Normal University, Hohhot 010022, China |
| Abstract: | Some η5-cyclopentadienyl cobalt dithiolene complexes CpCoS2C2R2 have been optimized at B3LYP/6-311++G(d) level. The optimized geometries agree well with experiment. The analyses of nature bond orbital and nucleus-independent chemical shift (NICS) at B3LYP/6-311++G(d) and GIAO-B3LYP/6-311++G(d) levels reveal the aromatic character of the η5-cyclopentadienyl cobalt dithiolene complexes. However, their aromaticity is weaker than that of the isolated . There are two reasons for the change of heterocyclic aromaticity of the metal dithiolene in the η5-cyclopentadienyl cobalt dithiolene complexes with respect to that of the isolated . The better equalization of bond lengths in the isolated cation is the first reason. The other reason is that the contribution to the NICS from the metallic cobalt atom is much larger in the isolated cation . The planar character of cyclopentadienyl is destroyed slightly in the complexes. At the same time, the size of cyclopentadienyl (Cp) becomes bigger than the isolated Cp−1 and this is caused by the cobalt atom in the pentagon. The π-electron delocalization causes stronger aromaticity of the Cp in the complexes than that of the isolated Cp−1. |
| Keywords: | Aromaticity NBO NICS Dithiolene |
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