Probing the influence of imidazolylidene- and triazolylidene-based carbenes on the catalytic potential of dioxomolybdenum and dioxotungsten complexes in deoxygenation catalysis.

We report the synthesis of dianionic OCO-supported NHC and MIC complexes of molybdenum and tungsten with the general formula (OCO)MO (OCO = bis-phenolate benzimidazolylidene M = Mo (1-Mo), bis-phenolate triazolylidene M = Mo (2-Mo), M = W (2-W) and bis-phenolate imidazolylidene, M = Mo (3-Mo), W (3-W)). These complexes are tested in the catalytic deoxygenation of nitroarenes using pinacol as a sacrificial oxygen atom acceptor/reducing agent to examine the influence of the carbene and the metal centre in this transformation. The results show that the molybdenum-based triazolylidene complex 2-Mo is by far the most active catalyst, and TOFs of up to 270 h are observed, while the tungsten analogues are basically inactive. Mechanistic studies suggest that the superiority of the triazolylidene-based complex 2-Mo is a result of a highly stable metal carbene bond, strongly exceeding the stability of the other NHC complexes 1-Mo and 3-Mo. This is proven by the structural isolation of a triazolylidene pinacolate complex (5-Mo) that can be thermally converted to a μ-oxodimolybdenum(V) complex 7-Mo. The latter complex is very oxophilic and stoichiometrically deoxygenates nitro- and nitrosoarenes at room temperature. In contrast, azoarenes are not reductively cleaved by 7-Mo, suggesting direct deoxygenation of the nitroarenes to the corresponding anilines with nitrosoarenes as intermediates. In summary, this work showcases the superior influence of MIC donors on the catalytic properties of early transition metal complexes.