skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on January 17, 2019

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

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:
Grant/Contract Number:
FG02-03ER15387; CHE-1461027; CHE-1531468
Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 37; Journal Issue: 3; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1417473