Kinetic Study of the Insertion and Deinsertion of Carbon Dioxide into fac-(CO)3(dppe)MnOR Derivatives
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- 作者：Donald J. Darensbourg ; Way-Zen Lee ; Andrea L. Phelps ; and Erin Guidry
- 刊名：Organometallics
- 出版年：2003
- 出版时间：December 22, 2003
- 年：2003
- 卷：22
- 期：26
- 页码：5585 - 5588
- 全文大小：111K
- 年卷期：v.22,no.26(December 22, 2003)
- ISSN：1520-6041
文摘
The insertion of carbon dioxide into theMn-O bond of fac-(CO)3(dppe)MnOCH3 (1) was observed to occur instantaneously at -78 
C by in situinfrared spectroscopy. The product of carboxylation of1, fac-(CO)3(dppe)MnOC(O)OCH3 (2), underwent decarboxylation with a first-order rate constant of 1.49 × 10-4s-1 at 23 C. The kinetic parameters for this process weredetermined by trapping the intermediate produced uponCO2 extrusion, complex 1, with COS to provide the verystable fac-(CO)3(dppe)MnSC(O)OCH3 (3) derivative. Thestructure of 3 was determined by single-crystal X-raydiffraction analysis, establishing the presence of theMn-S bond.
C by in situinfrared spectroscopy. The product of carboxylation of1, fac-(CO)3(dppe)MnOC(O)OCH3 (2), underwent decarboxylation with a first-order rate constant of 1.49 × 10-4s-1 at 23 C. The kinetic parameters for this process weredetermined by trapping the intermediate produced uponCO2 extrusion, complex 1, with COS to provide the verystable fac-(CO)3(dppe)MnSC(O)OCH3 (3) derivative. Thestructure of 3 was determined by single-crystal X-raydiffraction analysis, establishing the presence of theMn-S bond.