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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. Fri . "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 = {Fri Sep 15 00:00:00 EDT 2017},
month = {Fri Sep 15 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on September 15, 2018
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  • The reaction between molecular oxygen and coordination compounds of cobalt(II) with S-substituted N/sup 1/,N/sup 4/-di(salicylidene)isothiosemicarbazides in dimethyl sulfoxide solution was studied by the EPR method. It was found that paramagnetic monomeric adducts and diamagnetic ..mu..-peroxo-dimers are formed. The spin-Hamiltonian parameters of the EPR spectra of the initial cobalt complexes, as well as of the paramagnetic adducts were determined. The nature of the Co-O/sub 2/ bond is discussed.
  • A rapid, efficient procedure useful for the radiosynthesis of (Me-/sup 3/H)-MPDP+ ((methyl-/sup 3/H)-4-phenyl-2,3-dihydropyridinium species) is described. Hog liver microsomes or the highly purified flavin-containing monooxygenase from hog liver quantitatively biotransforms (Me-/sup 3/H)-MPTP to its corresponding radiolabeled N-oxide. For the small-scale synthesis required for radiolabeling procedures, this enzymatic process is superior to H/sub 2/O/sub 2/-mediated N-oxygenation of MPTP. In the presence of 0.5 mM NADPH, 4.5 mM n-octylamine, and 2 microCi (Me-/sup 3/H)-MPTP, the only product detected in extracts from incubations performed with hog liver microsomes or purified hog liver flavin-containing monooxygenase is (Me-/sup 3/H)-MPTP N-oxide. (Me-/sup 3/H)-MPTP N-oxide is almostmore » completely converted to (Me-/sup 3/H)-MPDP+ by the action of trifluoroacetic anhydride. This procedure has the advantage of using a commercially available tritiated starting material, efficient transformations, and easily accomplished purification to afford a rapid synthesis of (Me-/sup 3/H)-MPDP+.« less
  • The rate of carbonylation of methanol to methyl formate in methanol solutions of sodium methylate within the range 1-4 MPa and 80-110/sup 0/C obey the first-order equation with respect to the concentrations of sodium methylate, carbon monoxide, and methanol (k/sup ..-->../ = 10(/sup 7.84 +/- 0.23/) exp (-15,000 +/- 400)/RT, liters/sup 2//mole/sup 2/ x min). Under the same conditions the rate of decarbonylation of methyl formate is proportional to the concentrations of sodium methylate and methyl formate to the first power (k/sup ..-->../ = 10(/sup 13.43 +/- 0.37/) exp (-24,200 +/- 600)/RT, liter/mole x min). When methanol is replaced bymore » a form enriched (98%) with deuterium in the hydroxyl group,the kinetic isotope effect of the reaction is equal to one. It is concluded that the charge on the C-atom of the intermediate carbanion is too low for the splitting-off of H+ from the methanol molecule, introduced into the activated complex of nucleophilic attack of CH/sub 3/O- on CO and the stabilizing carbanion.« less
  • This paper studies the carbonylation reaction of methyl acetate (MA) with the formation of acetic anhydride, and also elucidates the mechanism of this reaction in the presence of a catalytic system including RhCl/sub 3/, Zn acetate, and MeI. The results obtained show that the metal halides studied can be arranged in order of activity and selectivity: RhCl/sub 3/ greater than RuCl/sub 3/ greater than PdCl/sub 2/. Small quantities of acetaldehyde, butyradehyde, acetic acid, and acetone are found in the reaction products.