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? 2 Coordination of Electron-Deficient Arenes with Group 6 Dearomatization Agents.

ABSTRACT: The exceptionally ?-basic metal fragments {MoTp-(NO)(DMAP)} and {WTp(NO)(PMe3)} (Tp = tris(pyrazolyl)borate; DMAP = 4-(N,N-dimethylamino)pyridine) form thermally stable ? 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 ? bond (nitriles, aldehydes, ketones, ester), ? 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 ? 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 ?-back-bonding interaction between the metal and aromatic ligand. While the molybdenum system did not form stable ? 2-arene complexes with the sulfones or ortho esters, it was capable of forming rare examples of stable ? 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.

PROVIDER: S-EPMC7810233 | BioStudies |

REPOSITORIES: biostudies

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