Experimental and Theoretical Investigations of Condensation and Disproportionation of Mn(bpy)Cl3(H2O) in Aqueous Solution

MnIII(bpy)Cl3H2O (Goodwin, H. A.; Sylva, R. N. Aust. J. Chem. 1965, 18, 1743) crystallizes in the triclinic space group P1, with a = 6.627(1) A, b = 9.991(7) A, c = 10.116(4) A, α = 84.38(4)°, β = 73.47(3)°, γ = 78.48(3)°, V = 629 A,3 and Z = 4. The MnIII ion has an octahedral surrounding distorted by a strong Jahn−Teller effect. Two chloride ions and the water molecule are involved into a network of hydrogen bonds. A careful study of aqueous solutions of MnIIILCl3H2O (L = bipyridine or phenanthroline) at different pH demonstrated the formation by condensation and disproportionation of [L2MnIIIO2MnIVL2](ClO4)3 (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623), [MnIV3O4L4(H2O)2](ClO4)4 (Sarneski, J. E.; et al. J. Am. Chem. Soc. 1990, 112, 7255) and [Mn4O6(bpy)6](ClO4)4 (Philouze, C.; et al. J. Am. Chem. Soc. 1994, 116, 8557). Condensation of MnLCl3H2O has been studied theoretically using partial charge models. It was possible to identify the mononuclear MnIII and MnIV species which are able to ...