Kinetic Study of the Insertion and Deinsertion of Carbon Dioxide into fac-(CO) 3(dppe)MnOR Derivatives

Donald J. Darensbourg, Way-Zen Lee, Andrea L. Phelps, Erin Guidry

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The insertion of carbon dioxide into the Mn - O bond of fac-(CO) 3(dppe)MnOCH 3 (1) was observed to occur instantaneously at -78 °C by in situ infrared spectroscopy. The product of carboxylation of 1, fac-(CO) 3(dppe)MnOC(O)OCH 3 (2), underwent decar-boxylation with a first-order rate constant of 1.49 × 10 -4 CO 2 at 23 °C. The kinetic parameters for this process were determined by trapping the intermediate produced upon CO 2 extrusion, complex 1, with COS to provide the very stable fac-(CO) 3(dppe)MnSC(O)OCH 3 (3) derivative. The structure of 3 was determined by single-crystal X-ray diffraction analysis, establishing the presence of the Mn - S bond.

Original languageEnglish
Pages (from-to)5585-5588
Number of pages4
JournalOrganometallics
Volume22
Issue number26
DOIs
Publication statusPublished - 2003 Dec 22

Fingerprint

carboxylation
Carbon Monoxide
Carbon Dioxide
carbon dioxide
insertion
infrared spectroscopy
trapping
Derivatives
Kinetics
single crystals
kinetics
products
diffraction
x rays
Carboxylation
Kinetic parameters
X ray diffraction analysis
Extrusion
Infrared spectroscopy
Rate constants

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Kinetic Study of the Insertion and Deinsertion of Carbon Dioxide into fac-(CO) 3(dppe)MnOR Derivatives. / Darensbourg, Donald J.; Lee, Way-Zen; Phelps, Andrea L.; Guidry, Erin.

In: Organometallics, Vol. 22, No. 26, 22.12.2003, p. 5585-5588.

Research output: Contribution to journalArticle

Darensbourg, Donald J. ; Lee, Way-Zen ; Phelps, Andrea L. ; Guidry, Erin. / Kinetic Study of the Insertion and Deinsertion of Carbon Dioxide into fac-(CO) 3(dppe)MnOR Derivatives. In: Organometallics. 2003 ; Vol. 22, No. 26. pp. 5585-5588.
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