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Title: Rapid and ordered carbonylation and oxygenation of a cobalt(II) methyl

Abstract

To MCoMe reacts rapidly with CO to give a low spin To MCo{C(O)Me}CO species, which is selectively oxygenated to form To MCoOAc.

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry; Ames Lab., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1394815
Report Number(s):
IS-J-9445
Journal ID: ISSN 1359-7345; CHCOFS
Grant/Contract Number:
AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 53; Journal Issue: 80; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Reinig, Regina R., Fought, Ellie L., Ellern, Arkady, Windus, Theresa L., and Sadow, Aaron D. Rapid and ordered carbonylation and oxygenation of a cobalt(II) methyl. United States: N. p., 2017. Web. doi:10.1039/C7CC06339C.
Reinig, Regina R., Fought, Ellie L., Ellern, Arkady, Windus, Theresa L., & Sadow, Aaron D. Rapid and ordered carbonylation and oxygenation of a cobalt(II) methyl. United States. doi:10.1039/C7CC06339C.
Reinig, Regina R., Fought, Ellie L., Ellern, Arkady, Windus, Theresa L., and Sadow, Aaron D. 2017. "Rapid and ordered carbonylation and oxygenation of a cobalt(II) methyl". United States. doi:10.1039/C7CC06339C.
@article{osti_1394815,
title = {Rapid and ordered carbonylation and oxygenation of a cobalt(II) methyl},
author = {Reinig, Regina R. and Fought, Ellie L. and Ellern, Arkady and Windus, Theresa L. and Sadow, Aaron D.},
abstractNote = {ToMCoMe reacts rapidly with CO to give a low spin ToMCo{C(O)Me}CO species, which is selectively oxygenated to form ToMCoOAc.},
doi = {10.1039/C7CC06339C},
journal = {ChemComm},
number = 80,
volume = 53,
place = {United States},
year = 2017,
month = 9
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on September 15, 2018
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  • The reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite was studied theoretically with periodic density functional theory calculations including dispersion forces and experimentally in a fixed bed flow reactor at pressures between 10 and 100 bar, dimethyl ether concentrations in CO between 0.2 and 2.0%, and at a temperature of 438 K. The theoretical study showed that the reaction of CO with surface methyl groups, the rate-limiting step, is faster in the eight-membered side pockets than in the twelve-membered main channel of the zeolite; the subsequent reaction of dimethyl ether with surface acetyl to form methyl acetatemore » was demonstrated to occur with low energy barriers in both the side pockets and in the main channel. Here, the present analysis has thus identified a path, where the entire reaction occurs favourably on a single site within the side pocket, in good agreement with previous experimental studies. The experimental study of the reaction kinetics was consistent with the theoretically derived mechanism and in addition revealed that the methyl acetate product inhibits the reaction – possibly by sterically hindering the attack of CO on the methyl groups in the side pockets.« less