[Co(NHC)(CO)3]: Isolation and Reactivity Study of a Model 17-Electron Species in the Oxo Process

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  • [Co(NHC)(CO)<sub>3</sub>]: Isolation and Reactivity Study of a Model 17-Electron Species in the Oxo Process

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[Co(L)(CO)3]2 (L = CO or PR3) catalyzed hydroformylation of olefins is among the most successful homogeneous organometallic catalysis. The bimetallic [Co(L)(CO)3]2 complex exists in equilibrium with its mononuclear 17-electron [Co(L)(CO)3] metalloradical. However, isolation of the mononuclear metalloradical is unknown, and hence the role of this species in the catalytic cycle is difficult to study. Herein, we report the isolation of [Co(L)(CO)3] using ring-expanded N-heterocyclic carbene (reNHC) ligands. Isolation of this complex enabled us to examine feasibility of putative termolecular H2 activation by the [Co(L)(CO)3] metalloradicals. The kinetic experiments revealed that [Co(reNHC)(CO)3] does not activate H2 via a previously proposed termolecular mechanism but via a bimolecular mechanism. The result obtained here will contribute to design a cobalt carbonyl complex that activates H2 under mild conditions and to develop a more energy efficient oxo process based on economical cobalt catalysts.

source:https://pubs.acs.org/doi/10.1021/acs.organomet.0c00765

Journal

  • Organometallics

    Organometallics 40 (4), 500-507, 2021-01-08

    American Chemical Society

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