Tungsten(VI) N-Heterocyclic Carbene Complexes: Synthetic, Structural, and Computational Study

The reaction of WOCl4 with 1,3-bis­(2,6-diisopropylphenyl)­imidazol-2-ylidene
(Idipp) leads to an orange solid whose spectroscopic data are consistent
with the 1:1 adduct [WOCl4(Idipp)]. Computational studies
at the DFT level further support this formulation. Exposure of this
compound to the atmosphere results in rapid hydrolysis to various
imidazolium salts. If air diffuses very slowly into solutions of [WOCl4(Idipp)], it also undergoes slow hydrolysis to form [WO2Cl2(Idipp)]. This has been crystallographically
characterized and is the first five-coordinate, 1:1 adduct of WO2Cl2. This complex has also been subject to DFT
calculations, and its metal–ligand bonding has been explored.
The carbene–metal interaction is primarily σ-donor in
nature. The mechanism of the hydrolysis has also been probed by computational
methods, revealing a plausible, low-energy reaction pathway.