Quantum chemical calculations of anion complex B_(12)H_x(NF2)_(12-x)~(2-), x = 9 - 12

摘要

The geometric, energetic, spectral and electronic properties of various isomers of B_(12)H_x(NF2)_(12-x)~(2-) anion complex with x = 9 - 12 have been studied using Density Functional Theory (B3LYP/6-311++G**). It was shown that the most stable isomers are characterized by the preference to form the most symmetric structures with uniformly distributed charge densities. However, when replacing a hydrogen atom with difluoramino group, an inductive effect occurs. NF2 group pulls a part of electron density that leads to the polarization of the boron core. Blue shifts in the IR spectrum compared to the vibrations of the free radical NF2 ranging from 5 to 69 cm~(-1) for the most stable isomers with the minimum total energy are characteristic and points to the stability of B_(12)H_x(NF2)_(12-x)~(2-) anions. The obtained results broaden the idea of aromaticity of Bi2H_(12)~(2-) anion and will be useful in synthesis of new B12H_(12)~(2-) derivatives.