Theoretical Design of Hexacoordinate Hypervalent Carbon Compounds by Analyzing Substituent Effects

• Published in: Bulletin of the Chemical Society of Japan 2011-05, Vol.84 (5), p.505-510
• Main Authors: Nakai, Hiromi, Okoshi, Masaki, Atsumi, Teruo, Kikuchi, Yasuaki, Akiba, Kin-ya
• Format: Article
• Language: English
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.20100358

A hexacoordinate hypervalent carbon compound with an ideal octahedral structure was proposed theoretically in a previous study (Chem. Phys. Lett. 2008, 460, 37). However, there is no report telling of success in synthesizing the compound and/or its derivatives. In order to perform a theoretical design for stronger hypervalent bonds, the present study systematically investigated the substituent effects at the para position of phenyl groups of axial C–C and equatorial C–O bonds by adopting 14 functional groups involving both electron-donating and -withdrawing groups. The results showed that the substituent effect at the former position is more influential than that at the latter. In the former case, a good correlation between the C–C and C–O distances is found and the hypervalent C–O bonds are strengthened as the substituent becomes more electron-withdrawing. In the latter case, both electron-donating and -withdrawing groups slightly weaken the hypervalent C–O bonds.