Evaluation of Cobalt Complexes Bearing Tridentate Pincer Ligands for Catalytic C-H Borylation

Cobalt(II) dichloride complexes supported by a variety of neutral, tridentate pincer ligands have been prepared and, following in situ activation with NaBEt₃H, evaluated for the catalytic borylation of 2-methylfuran, 2,6-lutidine, and benzene using both HBPin and B₂Pin₂ (Pin = pinacolate) as boron sources. Preparation of well-defined organometallic compounds in combination with stoichiometric experiments with HBPin and B₂Pin₂ provided insight into the nature and kinetic stability of the catalytically relevant species. In cases where sufficiently electron donating pincers are present, such as with bis(phosphino)pyridine chelates, Co(III) resting states are preferred and catalytic C-H borylation is efficient. Introduction of a redox-active subunit into the pincer reduces its donating ability and, as a consequence, the accessibility of a Co(III) resting state. In these cases, unusual mixed-valent μ-hydride cobalt complexes have been crystallographically and spectroscopically characterized. These studies have also shed light on the active species formed during in situ activated cobalt alkene hydroboration catalysis and provide important design criteria in base metal catalyzed C-B bond forming reactions. (Chemical Presented).