C−H Deprotonation and C=C Hydrogenation of N‐Heterocyclic Olefin with Calcium Hydride Complexes: Cooperative Ca−H−Ca Bridge versus Terminal Ca−H bond

Abstract

AbstractMonomeric calcium hydride intermediates with reactive terminal Ca−H bond were recently proposed to deprotonate N‐heterocyclic olefin ligands upon moderate heating with dimeric amidinate calcium hydride complexes. In contrast, extensive dispersion‐corrected DFT calculations disclose the frustrated Lewis pair (FLP) like reactivity of cooperative Ca−H−Ca bridges for stoichiometric C−H deprotonation and kinetically more favorable catalytic C=C hydrogenation with pressured H2, thus providing useful insights for metal hydride based hydrogenation catalysts.