Kinetic study of the insertion and deinsertion of carbon dioxide into fac-(CO)3(dppe)MnOR derivatives

被引：39

作者：

Darensbourg, DJ ^{[1
]}

Lee, WZ ^{[1
]}

Phelps, AL ^{[1
]}

Guidry, E ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA

来源：

ORGANOMETALLICS | 2003年 / 22卷 / 26期

关键词：

D O I：

10.1021/om034087j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The insertion of carbon dioxide into the Mn-O bond of fac-(CO)(3)(dppe)MnOCH3 (1) was observed to occur instantaneously at -78 degreesC by in situ infrared spectroscopy. The product of carboxylation of 1, fac-(CO)(3)(dppe)MnOC(O)OCH3 (2), underwent decarboxylation with a first-order rate constant of 1.49 x 10(-4) s(-1) at 23 degreesC. The kinetic parameters for this process were determined by trapping the intermediate produced upon CO2 extrusion, complex 1, with COS to provide the very stable fac-(CO)(3)(dppe)MnSC(O)OCH3 (3) derivative. The structure of 3 was determined by single-crystal X-ray diffraction analysis, establishing the presence of the Mn-S bond.

引用

页码：5585 / 5588

页数：4

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