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Unexpected 1,2‐Migration in Metallasilabenzenes: Theoretical Evidence for Reluctance of Silicon to Participate in π Bonding
Author(s) -
Huang Ying,
Zhu Jun
Publication year - 2015
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201402992
Subject(s) - magnetic reluctance , silicon , materials science , psychology , forensic engineering , engineering , mechanical engineering , optoelectronics , magnet
Density functional theory (DFT) calculations were carried out to investigate the 1,2‐migration in metallasilabenzenes. The results suggested that the chloride migration of metallabenzenes is unfavorable due to the loss of aromaticity in the nonaromatic analogues. In sharp contrast, such a migration in metallasilabenzenes is favorable due to the reluctance of silicon to participate in π bonding. The migration of hydride and methyl group from the metal center to the silicon atom in metallasilabenzenes is computed to be also feasible. In addition, the π donor ligand and the third row transition metal can stabilize metallasilabenzenes. Thus, such a migration becomes less favorable thermodynamically and kinetically. These findings could be very helpful for synthetic chemists to realize the first metallasilabenzene.