Infrared photodissociation spectroscopy of V+(H2O)n (n=2-8): Coordinative saturation of V+ with four H2O molecules

The V+(H2O)(n) ions with n = 2-8 are studied by infrared (IR) photodissociation spectroscopy. The IR spectra indicate that H2O molecules are allowed to bind directly to V+ until the completion of a 4-coordinated structure and additional molecules are forced to occupy outer solvation shells. Density functional theory calculations suggest that one empty orbital in V+ (3d(4)) before coordination can be identified with the 3d(x2-y2) orbital, which provides four sites of lower electron density along the x and y axes. This results in a strong interaction with only four H2O molecules, and thus, a stable square-planar V+(H2O)(4) complex. (C) 2009 Elsevier B. V. All rights reserved.