title: Effective Pincer Cobalt Precatalysts for Lewis Acid Assisted CO2 Hydrogenation.
abstract: The pincer ligand MeN[CH2CH2(P(i)Pr2)]2 ((iPr)PNP) was employed to support a series of cobalt(I) complexes, which were crystallographically characterized. A cobalt monochloride species, ((iPr)PNP)CoCl, served as a precursor for the preparation of several cobalt precatalysts for CO2 hydrogenation, including a cationic dicarbonyl cobalt complex, [((iPr)PNP)Co(CO)2](+). When paired with the Lewis acid lithium triflate, [((iPr)PNP)Co(CO)2](+) affords turnover numbers near 30 000 (at 1000 psi, 45 °C) for CO2-to-formate hydrogenation, which is a notable increase in activity from previously reported homogeneous cobalt catalysts. Though mechanistic information regarding the function of the precatalysts remains limited, multiple experiments suggest the active species is a molecular, homogeneous [((iPr)PNP)Co] complex.
authors.affiliation: Department of Chemistry, University of Missouri , Columbia, Missouri 65211, United States.
authors.forename: Ariana Z
authors.initials: AZ
authors.lastname: Spentzos
authors.affiliation: Department of Chemistry, University of Missouri , Columbia, Missouri 65211, United States.
authors.forename: Charles L
authors.initials: CL
authors.lastname: Barnes
authors.affiliation: Department of Chemistry, University of Missouri , Columbia, Missouri 65211, United States.
authors.forename: Wesley H
authors.initials: WH
authors.lastname: Bernskoetter