Elucidation of hydrolysis reaction mechanism of tungsten hexafluoride (WF6) using first-principles calculations

摘要

We identify hydrolysis reaction mechanism of water-reactive WF6 and its accompanying intermediates using first-principles calculations. For the purpose, we evaluate activation and free energy diagrams of elementary reaction steps. We find that WF6, WOF4, and WO2F2 form stable adducts, which quickly reacts with H2O by substituting the ligand F. Gaseous WOF4, WO2F2, WO3 are predicted as unstable in the increasing order, but polymerization reduces their instability, leading to solidification. In overall reaction, WOF4 hydrolysis is the bottleneck due to significantly higher activation barrier of trans isomeric complex than cis counterpart. (C) 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.