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Computational Study of Methane C−H Activation by First-Row Late Transition Metal L_nM═E (M: Fe, Co, Ni) Complexes

Aaron W. Pierpont and Thomas R. Cundari*

Department of Chemistry and Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas, P.O. Box 305070, Denton, Texas 76203-5070

Inorg. Chem., 2010, 49 (5), pp 2038–2046

DOI: 10.1021/ic901250z

Publication Date (Web): August 21, 2009

*To whom correspondence should be addressed. E-mail: t@unt.edu.

Abstract

Methane functionalization via L_nM═E active species (L_n = β-diketiminate, dihydrophosphinoethane; M = Fe−Ni, E = NCF₃, NCH₃, O) through a hydrogen atom abstraction (HAA)/radical rebound (RR) mechanism is calculated to be thermodynamically and kinetically feasible. The enthalpies of each reaction decrease in the order Fe > Co > Ni and with the proximity of CF₃ supporting ligand substituents (“fluorination”) to the metal center. For HAA, lower abstraction enthalpies were calculated for L_n = β-diketiminate and E = NCF₃ rather than dhpe and NCH₃, respectively, whereas the opposite trend was found for RR enthalpies. The overall functionalization thermodynamics were optimal for L_n = β-diketiminate and E = NCH₃, with similar enthalpies for E = O when M = Ni. The HAA kinetics further implicate fluorinated (β-diket)Ni═O as the most promising methane functionalization complexes, with calculated activation barriers as low as 8.1 kcal mol⁻¹.

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This article has been cited by 1 ACS Journal articles (1 most recent appear below).

Non-redox Oxy-Insertion via Organometallic Baeyer–Villiger Transformations: A Computational Hammett Study of Platinum(II) Complexes
Travis M. Figg, Thomas R. Cundari, and T. Brent Gunnoe
Organometallics2011 Article ASAP
- Non-redox Oxy-Insertion via Organometallic Baeyer–Villiger Transformations: A Computational Hammett Study of Platinum(II) Complexes
  Travis M. Figg, Thomas R. Cundari, and T. Brent Gunnoe
  Organometallics2011 Article ASAP
  A Hammett analysis of platinum-mediated oxy-insertion into Pt–aryl bonds is performed using DFT calculations. Modeled transformations involve the conversion of cationic PtII-aryl complexes [(Xbpy)Pt(R)(OY)]+ (R = p-X-C6H4; Y = 4-X-pyridine; Xbpy = 4,4′-X-...
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History

Published In Issue March 01, 2010
Article ASAPAugust 21, 2009
Received: June 30, 2009

Article

Computational Study of Methane C−H Activation by First-Row Late Transition Metal L_nM═E (M: Fe, Co, Ni) Complexes

Abstract

Citing Articles

Non-redox Oxy-Insertion via Organometallic Baeyer–Villiger Transformations: A Computational Hammett Study of Platinum(II) Complexes