Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

Lopez, Kent G.; Cundari, Thomas R.; Gary, J. Brannon

doi:10.1021/acs.organomet.7b00715

Title: Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

Journal Article · Wed Jan 17 00:00:00 EST 2018 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.7b00715· OSTI ID:1417473

Lopez, Kent G. ^[1];

^[1]; Gary, J. Brannon ^[2]

Univ. of North Texas, Denton, TX (United States). Center for Advanced Scientific Computing and Modeling (CASCaM)
Univ. of North Texas, Denton, TX (United States). Center for Advanced Scientific Computing and Modeling (CASCaM); Stephen F. Austin State Univ., Nacogdoches, TX (United States). Dept. of Chemistry & Biochemistry

A computational study of the experimentally proposed mechanism of alkyne diboration by a PDICo complex yielded two fundamental catalytic steps that undergo remarkable electronic changes, PDI = bis(imino)-pyridine. The reactions are envisaged via DFT (density functional theory) and MCSCF (multi-configuration self-consistent field) simulations as (i) a cooperative metal+ligand oxidative addition, and (ii) a sigma-bond metathesis induced ligand-to-metal charge transfer. Analysis of the bonding of pertinent intermediates/TSs also yielded important insight that may be illuminating with regards to the larger field of green catalysis that seeks to ennoble base metals through synergy with potentially redox non-innocent (RNI) ligands. For the present case, massive changes in electronic structure do not incur massive energetic penalties. Finally, in conjunction with previous research, one may postulate that structural and energetic “fluidity” among several electronic states of RNI-M_3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.

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