Contribution from the Institut für Anorganische Chemie and the Laboratorium für Kristallographie, Universitat Bern, Bern, Switzerland [(phen)2MnIV(/t-0)2Mnni(phen)2](PF6)3*CH3CN and [(phen)2MnIV(M-0)2MnIV(phen)2](a04)4-CH3CN (phen = 1,10-Phenanthroline): Crystal Structure Analyses at 100 K, Interpretation of Disorder, and Optical, Magnetic, and Electrochemical Results

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The rate of electron self-exchange of Mn(CNC(CH3)3)6+/2+ and Mn(CNC6Hn)6+/2+ as the BF4' salts has been measured by 55Mn NMR line broadening as a function of pressure, temperature, and concentration in acetonitrile, bromobenzene, benzonitrile, acetone, diethyl ketone, methanol, ethanol, methylene chloride, and trimethyl phosphate, and various binary mixtures of methylene chloride, bromobenzene, and acetonitrile. The values of AV* obtained are negative and cover a range of ca. 12 cm1 23/mol, which is limited by ion pairing in the solvents of lower dielectric constant. The variation of the ambient pressure rate constant with solvent is qualitatively different for the Mn(CNC(CH3)3)6+/2+ reaction than was observed for the Mn(CNC6Hn)6+/2+ reaction. This is taken as further evidence for a significant influence of rather subtle differences in solvation on the molecular level that are not approximated by dielectric continuum models.