Solution chemistry of element 105. Pt. 1. Hydrolysis of group 5 cations: Nb, Ta, Ha and Pa

摘要

Relativistic molecular orbital calculations of the electronic structure of hydrated and hydrolyzed complexes have been performed for group 5 elements Nb, Ta, Ha and their pseudohomology, Pa. On their basis, relative values of the free energy changes and constants of hydrolysis reactions were defined. These results show that hydrolysis decreases in the order Nb>Ta>Ha>>Pa, which for Nb, Ta and Pa is in agreement with experiment. A decisive factor in the process turned out to be a predominant electrostatic metal-ligand interaction. (orig.)