Y. Inada, T. Sugata, K. Ozutsumi
Apr 1, 1998
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Journal
Inorganic Chemistry
Abstract
The solution structure of the manganese(II) ion in acetonitrile (methyl cyanide, AN) has been determined by an X-ray diffraction technique: there are 6.0 ± 0.2 Mn−N bonds and the Mn−N bond length is 221 ± 1 pm. The solvation structures of the manganese(II) ion in propiononitrile (ethyl cyanide, PN), butyronitrile (propyl cyanide, BuN), isobutyronitrile (isopropyl cyanide, iBuN), valeronitrile (butyl cyanide, VN), and benzonitrile (phenyl cyanide, BzN) have been determined by extended X-ray absorption fine structure spectroscopy. The manganese(II) ion in all of these nitriles is six-coordinate octahedral with an Mn−N bond length of 221 ± 1 pm. The activation parameters for solvent exchange on the manganese(II) ion in the six nitriles have been determined by the nuclear magnetic resonance line broadening technique at various temperatures and pressures. The values of the rate constant ( , s-1), activation enthalpy (ΔH⧧, kJ mol-1), activation entropy (ΔS⧧, J mol-1 K-1), and activation volume (ΔV⧧, cm3 mol-1)...