Toward Rational Design of 3d Transition Metal Catalysts for CO2 Hydrogenation Based on Insights into Hydricity-Controlled Rate-Determining Steps.

Carbon dioxide functionalization attracts much interest due to the current environmental and energy challenges. Our earlier work (Mondal, B.; Neese, F.; Ye, S. Inorg. Chem. 2015, 54, 7192-7198) demonstrated that CO2 hydrogenation mediated by base metal catalysts M(H)(η(2)-H2)(PP3(Ph)) (M = Co(III) and Fe(II), n = 1, 2; PP3(Ph) = tris(2-(diphenylphosphino)phenyl)phosphine) features discrete rate-determining steps (RDSs). Specifically, the reaction with Co(III)(H)(η(2)-H2)(PP3(Ph)) passes through a hydride-transfer RDS, whereas the conversion with Fe(II)(H)(η(2)-H2)(PP3(Ph)) traverses a H2-splitting RDS. More importantly, we found that the nature and barrier of the RDS likely correlate with the hydride affinity or hydricity of the dihydride intermediate M(H)2(PP3(Ph)) generated by H2-splitting. In the present contribution, following this notion we design a series of potential Fe(II) and Co(III) catalysts, for which the respective dihydride species possess differential hydricities, and computationally investigated their reactivity toward CO2 hydrogenation. Our results reveal that lowering the hydrictiy of Co(III)(H)2(PP3(Ph)) by introducing anionic anchors in PP3(Ph) dramatically decreases the hydride-transfer RDS barrier, as shown for the enhanced reactivity of Co(H)(η(2)-H2)(CP3(Ph)) and Co(H)(η(2)-H2)(SiP3(Ph)) (CP3(Ph) = tris(2-(diphenylphosphino)phenyl)methyl, SiP3(Ph) = tris(2-(diphenylphosphino)phenyl)silyl), while the same ligand modification increases the H2-splitting RDS barriers for [Fe(H)(η(2)-H2)(CP3(Ph))] and [Fe(H)(η(2)-H2)(SiP3(Ph))] relative to that for Fe(H)(η(2)-H2)(PP3(Ph)). Conversely, upon increasing the hydricity of [Fe(II)(H)2(PP3(Ph))] by adding an electron-withdrawing group to PP3(Ph), the transformation with Fe(H)(η(2)-H2)(PP3(PhNO2)) (PP3(PhNO2) = tris(2-(diphenylphosphino)-4-nitrophenyl)phosphine) is predicted to encounter a lower barrier for H2-splitting and a higher barrier for hydride transfer than those for Fe(H)(η(2)-H2)(PP3(Ph)). Thus, we have shown that hydricity can be used as a guide to direct the rational design and development of more efficient catalysts.