CaltechAUTHORS
  A Caltech Library Service

Using Reduced Catalysts for Oxidation Reactions: Mechanistic Studies of the “Periana-Catalytica” System for CH_4 Oxidation

Mironov, Oleg A. and Bischof, Steven M. and Konnick, Michael M. and Hashiguchi, Brian G. and Ziatdinov, Vadim R. and Goddard, William A., III and Ahlquist, Mårten and Periana, Roy A. (2013) Using Reduced Catalysts for Oxidation Reactions: Mechanistic Studies of the “Periana-Catalytica” System for CH_4 Oxidation. Journal of the American Chemical Society, 135 (39). pp. 14644-14658. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20131205-135636346

[img]
Preview
PDF - Supplemental Material
See Usage Policy.

538Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

11Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

11Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20131205-135636346

Abstract

Designing oxidation catalysts based on CH activation with reduced, low oxidation state species is a seeming dilemma given the proclivity for catalyst deactivation by overoxidation. This dilemma has been recognized in the Shilov system where reduced Pt^(II) is used to catalyze methane functionalization. Thus, it is generally accepted that key to replacing Pt^(IV) in that system with more practical oxidants is ensuring that the oxidant does not over-oxidize the reduced Pt^(II) species. The “Periana-Catalytica” system, which utilizes (bpym)Pt^(II)Cl_2 in concentrated sulfuric acid solvent at 200 °C, is a highly stable catalyst for the selective, high yield oxy-functionalization of methane. In lieu of the over-oxidation dilemma, the high stability and observed rapid oxidation of (bpym)Pt^(II)Cl_2 to Pt^(IV) in the absence of methane would seem to contradict the originally proposed mechanism involving CH activation by a reduced Pt^(II) species. Mechanistic studies show that the originally proposed mechanism is incomplete and that while CH activation does proceed with Pt^(II) there is a solution to the over-oxidation dilemma. Importantly, contrary to the accepted view to minimize Pt^(II) overoxidation, these studies also show that increasing that rate could increase the rate of catalysis and catalyst stability. The mechanistic basis for this counterintuitive prediction could help to guide the design of new catalysts for alkane oxidation that operate by CH activation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja404895zDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja404895zPublisherArticle
ORCID:
AuthorORCID
Mironov, Oleg A.0000-0002-9787-944X
Goddard, William A., III0000-0003-0097-5716
Periana, Roy A.0000-0001-7838-257X
Additional Information:© 2013 American Chemical Society. Received: May 22, 2013. Published: August 8, 2013. The authors acknowledge the Center for Catalytic Hydrocarbon Functionalization, a DOE Energy Frontier Research Center (DOE DE-SC000-1298), for funding S.M.B., M.M.K., and B.G.H. Chevron Technology Corporation provided partial funding for O.A.M., V.R.Z., W.A.G., M.A., and R.A.P. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Center for Catalytic Hydrocarbon FunctionalizationUNSPECIFIED
Department of Energy (DOE) Energy Frontier Research CenterDE-SC000-1298
Chevron Technology CorporationUNSPECIFIED
Issue or Number:39
Record Number:CaltechAUTHORS:20131205-135636346
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20131205-135636346
Official Citation: Using Reduced Catalysts for Oxidation Reactions: Mechanistic Studies of the “Periana-Catalytica” System for CH4 Oxidation Oleg A. Mironov, Steven M. Bischof, Michael M. Konnick, Brian G. Hashiguchi, Vadim R. Ziatdinov, William A. Goddard, III, Mårten Ahlquist, and Roy A. Periana Journal of the American Chemical Society 2013 135 (39), 14644-14658
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42862
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:05 Dec 2013 23:00
Last Modified:03 Oct 2019 06:02

Repository Staff Only: item control page