Exceptionally Long C-C Single Bonds in Diamino-o-carborane as Induced by Negative Hyperconjugation

The synthesis of a series of 1,2-diamino-o-carboranes (1-4) is reported. The molecular structures of these diamino-o-carboranes are remarkable as the inner-cluster C-C bonds are all ultra-long (162.7-193.1 pm) and vary substantially with small variations in the substituents. The results of quantum mechanical investigations suggest that the origin of the bond elongation is significant in-plane negative hyperconjugation of lone pairs of the nitrogen substituents with the sigma* orbitals of the C-C bonds in o-carboranes.