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

ABSTRACT: 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

SUBMITTER: Smith JA 

PROVIDER: S-EPMC7810233 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature