Unexpected 1,2-migration in metallasilabenzenes: theoretical evidence for reluctance of silicon to participate in π bonding.
Chem Asian J
; 10(2): 405-10, 2015 Feb.
Article
in En
| MEDLINE
| ID: mdl-25385431
ABSTRACT
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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Chem Asian J
Year:
2015
Document type:
Article