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