148447-59-0Relevant academic research and scientific papers
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
, p. 5585 - 5588 (2003)
The insertion of carbon dioxide into the Mn - O bond of fac-(CO) 3(dppe)MnOCH3 (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)OCH3 (2), underwent decar-boxylation with a first-order rate constant of 1.49 × 10 -4 CO2 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)OCH3 (3) derivative. The structure of 3 was determined by single-crystal X-ray diffraction analysis, establishing the presence of the Mn - S bond.
Use of the aqua complex [fac-Mn(CO)3(dppe)OH2]BF4 for the preparation of a series of fac-Mn(CO)3(dppe)Z and [fac-Mn(CO)3(dppe)Z]BF4 complexes. X-ray crystal structures of three representative examples
Becker, Thomas M.,Krause Bauer, Jeanette A.,Homrighausen, Craig L.,Orchin, Milton
, p. 97 - 104 (2007/10/03)
The aqua ligand in the titled complex (prepared by a simple two-step, high-yield synthesis) is readily replaced by the desired anionic ligand Z-, to give a six-coordinate neutral species fac-Mn(CO)3(dppe)Z. Examples of such complexes where Z=O-NO2, CN, OMe, OC(O)OMe, and OS(O)2CF3 (OTf) are reported herein. Neutral ligands also replace the aqua ligand to give ionic complexes [fac-Mn(CO)3(dppe)Z]BF4. Examples where Z=2,6-dimethylphenyl (xylyl) isocyanide, acetonitrile, benzonitrile, and acrylonitrile are also reported herein. Crystal structures of fac-Mn(CO)3(dppe)NO3 (2), [fac-Mn(CO)3(dppe)(xylyl-NC)]BF4 (7), and [fac-(CO)3Mn(dppe)(PhCN)]BF4 (9), are reported.
