X-Ray and X-ray Photoelectron Spectroscopy Studies of the Electronic Structure of Borane Derivatives

This paper reviews the results of electronic structure studies of a number of typical members of borane series by X-ray and X-ray photoelectron spectroscopy using quantum chemical calculations. Fragment analysis of the molecular orbital structure is given. The nature of chemical interaction in boron cluster compounds is studied on models: simple molecules NH3, BH3, and BF3 and their adducts NH3⋅BH3 and NH3⋅BF3⋅. The electronic structure of B10H12L2 type compounds with Lewis bases L = NH3, (CH3)2S, (C6H5)3P is analyzed. The complexes are considered in terms of the concept of donor–acceptor interactions between the fragments. The donor–acceptor bond has contributions from both occupied and vacant acceptor orbitals. X-ray photoelectron data on the charged states of atoms in the compounds are overviewed. Electron distribution in complex compounds with transition metals [(1,2-B9C2H11)2M]–, M = FeIII, CoIII, NiIII, and NiIV and chain type polycobaltocarborane anions {[(3)-1,2-B9C2H11]2Con[(3,6)-1,2-B8C2H10]n-1}n–, n = 2-7, is considered.