Pyridine and 2,2′-bipyridyl derivatives of nitratopentacarbonylmanganese(I)

Abstract

The reactions of nitratopentacarbonylmanganese(I) with pyridine (Py) and 2,2′-bipyridyl (bipy) yield the disubstituted derivatives Mn(CO)₃Py₂NO₃ and Mn(CO)₃bipyNO₃; the nitrato-group remains bonded to the metal. The increase in electrical conductivity with time of nitromethane solutions of the complexes is explained in terms of solvent replacement of the nitrate ion. Further substitution with pyridine and triphenylphosphine (PPh₃) produces the ionic complexes [Mn(CO)₃bipyPy]NO₃, [Mn(CO)₃bipyPPh₃]NO₃, and [Mn(CO)₂bipy(PPh₃)₂]NO₃. Decomposition of Mn(CO)₃bipyNO₃ gives the non-carbonyl complex Mn(bipy)₂(NO₃)₂, isomers of which are prepared from anhydrous and hydrated manganese nitrate. On the basis of infrared spectra, structures for the carbonyl and non-carbonyl products are suggested.