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The reaction of WOCl 4 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 [WOCl 4 (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 [WOCl 4 (Idipp)], it also undergoes slow hydrolysis to form [WO 2 Cl 2 (Idipp)]. This has been crystallographically characterized and is the first five-coordinate, 1:1 adduct of WO 2 Cl 2 . 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.

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