The Undecahydrodecaborate Anion B_(10)H_(11)~- as the Starting Reagent in Exopolyhedral Substitution and Complexation: Theoretical and Experimental Prerequisites

摘要

Using the electron density functional theory (B3LYP approximation) with the 6-31G* basis set, the potential energy surface of the undecahydrodecaborate anion B_(10)H_(11)~- was calculated and the activation energies and the activation barriers for the elementary reactions of proton H* migration around the boron polyhedron were estimated. Analysis of the calculation results in comparison with the experimental data accumulated recently implies that the salts of the B_(10)H_(11)~- anion represent a new type of starting compounds for exopolyhedral substitution and complexation involving decaborate anions. Of particular interest is the targeted preparation of isomers of metal complexes containing a decaborate anion depending on the use of B_(10)H_(10)~(2-) or B_(10)H_(11)~(2-) as the starting reagent. Certain trends in the reactivity of B_(10)H_(10)~- and B_(10)H_(11)~- anions can be explained in terms of the simple analysis of Mulliken charge distribution on atoms.