SYNTHESIS, SPECTRAL PROPERTIES, AND REACTIONS OF MANGANESE AND RHENIUM PENTACARBONYL PHOSPHINE AND PHOSPHITE CATION DERIVATIVES AND RELATED COMPLEXES
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abstract
The synthesis of a variety of monosubstituted manganese and rhenium carbonyl cationic species of the form [M(CO)5L] [PFe] is reported, where L = group 5A ligands. Preparation of these derivatives was accomplished either through the reaction of [LM(CO)4]- with C2H5O2CCl followed by treatment with HBF4 (or BF3) or by thermal replacement of CH3CN in the M(CO)5(CH3CN)+ derivative. The latter procedure was shown to be the method of choice. The reaction of these pentacarbonyl derivatives with CH3NH2 to form cis- [Mn(CO)4(L)C(O)NEICH3] is discussed in relation to other nucleophilic reactions at the carbonyl carbon atom. Displacement of CO ligands from the Mn(CO)5(CH3CN)+ species in solution by pyridine, phosphines, and CH3CN is also reported. In some of these multisubstituted species, exchange of the bound CH3CN ligands was observed. The CO stretching force constants were calculated for all the cationic species prepared. In the pentacarbonylmanganese phosphine derivatives the axial CO force constant, k1, was quite similar to the equatorial CO force constant, k2. This result is discussed in terms of a direct donation of phosphorus electrons into the orbitals of the equatorial CO ligands. 1975, American Chemical Society. All rights reserved.
