η Coordination of Electron-Deficient Arenes with Group 6 Dearomatization Agents

The exceptionally π-basic metal fragments {MoTp-(NO)(DMAP)} and {WTp(NO)(PMe₃)} (Tp = tris(pyrazolyl)borate; DMAP = 4-(N,N-dimethylamino)pyridine) form thermally stable η ²-coordinated complexes with a variety of electron-deficient arenes. The tolerance of substituted arenes with fluorine-containing electron withdrawing groups (EWG; -F, -CF₃, -SF₅) is examined for both the molybdenum and tungsten systems. When the EWG contains a π bond (nitriles, aldehydes, ketones, ester), η ² coordination occurs predominantly on the nonaromatic functional group. However, complexation of the tungsten complex with trimethyl orthobenzoate (PhC(OMe)₃) followed by hydrolysis allows access to an η ²-coordinated arene with an ester substituent. In general, the tungsten system tolerates sulfur-based withdrawing groups well (e.g., PhSO₂Ph, MeSO₂Ph), and the integration of multiple electron-withdrawing groups on a benzene ring further enhances the π-back-bonding interaction between the metal and aromatic ligand. While the molybdenum system did not form stable η ²-arene complexes with the sulfones or ortho esters, it was capable of forming rare examples of stable η ²-coordinated arene complexes with a range of fluorinated benzenes (e.g., fluorobenzene, difluorobenzenes). In contrast to what has been observed for the tungsten system, these complexes formed without interference of C-H or C-F insertion.