Effect of Pincer Methylation on the Selectivity and Activity in (PNP)Cobalt-Catalyzed C(sp2)-H Borylation.

Cobalt complexes supported by a tetramethylated PNP pincer ligand (Me4 iPrPNP = 2,6-(iPr2PCMe2)2(C5H3N)) have been synthesized and structurally characterized. Examples include cobalt(I)-choride, -methyl, -aryl and -benzofuranyl derivatives. The performance of these compounds was evaluated in the catalytic borylation of fluorinated arenes using B2Pin2 as the boron source. While P-C bond cleavage, a known deactivation pathway in [(PNP)Co]-catalyzed borylation was suppressed, the overall activity and selectivity of the borylation of fluoroarenes was reduced as compared to the previously reported [(PNP)Co] catalyst lacking isopropylene spacers. Stoichiometric reactions support an increased barrier for oxidative addition to cobalt(I), a result of the increased steric profile and decreased conformational flexibility of the pincer resulting from methylation distal to the active site. With a more activated substrate such as benzofuran, catalytic borylation with cobalt(I) precatalysts and HBPin was observed. Monitoring the progress of the reaction by NMR spectroscopy revealed the presence of cobalt(III) intermediates during the course of the borylation, supporting a cobalt(I)-(III) redox cycle.