Carbide formation via carbon monoxide dissociation across a W[triple bond]W bond

The dissociative adsorption of carbon monoxide is the putative initial step in the heterogeneous Fischer-Tropsch (F-T) process, the catalytic conversion of synthesis gas (CO/H[sub 2]) to hydrocarbons and oxygenates. Few homogeneous analogues of CO dissociation exist, and these reactions often follow somewhat convoluted pathways or rely on CO disproportionations to provide carbide and CO[sub 2]. In attempting to prepare monomeric W(III) derivatives coordinated by silox ([sup t]Bu[sub 3]SiO[sup [minus]]), dinuclear complexes containing the inherently stable (W[triple bond]W)[sup 6+] unit were instead formed. Fortunately, the steric and electronic properties of silox permitted observation of intriguing C[triple bond]O and C[triple bond]NAr bond cleavages by the W[sub 2] triple bond, transformations that differ significantly from the reactivity of related group 6 species studied by Chisholm et al. 27 refs., 3 figs.