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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:
 [1]; ORCiD logo [1];  [2]
  1. Univ. of North Texas, Denton, TX (United States). Center for Advanced Scientific Computing and Modeling (CASCaM)
  2. 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:
Research Org.:
Univ. of North Texas, Denton, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); 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.
Lopez, Kent G., Cundari, Thomas R., & Gary, J. Brannon. Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study. United States. doi:10.1021/acs.organomet.7b00715.
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. doi:10.1021/acs.organomet.7b00715. https://www.osti.gov/servlets/purl/1417473.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 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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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.