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

Abstract

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.

Authors:

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

Publication Date:: 2018-01-17

Research Org.:: Univ. of North Texas, Denton, TX (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:: 1417473

Grant/Contract Number:: FG02-03ER15387; CHE-1461027; CHE-1531468

Resource Type:: Accepted Manuscript

Journal Name:: Organometallics

Additional Journal Information:: Journal Volume: 37; Journal Issue: 3; Journal ID: ISSN 0276-7333

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Lopez, Kent G., Cundari, Thomas R., and Gary, J. Brannon. Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.organomet.7b00715.

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                    Lopez, Kent G., Cundari, Thomas R., & Gary, J. Brannon. Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study.  United States.  https://doi.org/10.1021/acs.organomet.7b00715

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                    Lopez, Kent G., Cundari, Thomas R., and Gary, J. Brannon. Wed .  
"Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study".  United States.  https://doi.org/10.1021/acs.organomet.7b00715.  https://www.osti.gov/servlets/purl/1417473.

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@article{osti_1417473,

  title        = {Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study},

  author       = {Lopez, Kent G. and Cundari, Thomas R. and Gary, J. Brannon},

  abstractNote = {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-M3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.},

  doi          = {10.1021/acs.organomet.7b00715},

  journal      = {Organometallics},

  number       = 3,

  volume       = 37,

  place        = {United States},

  year         = {2018},

  month        = {1}

}

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Figures / Tables:

Figure 1: uB3LYP/6-31G(d,p)-optimized geometry of ³PDICo(C≡CMe). Bond lengths in Å, angles in ⁰. A superscript prefix numeral indicates the multiplicity. Co = salmon, N = magenta, C = yellow, H = blue.

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