Triheteropolyanions containing copper(II), manganese(II), or manganese(III)

• Published in: Journal of inorganic & nuclear chemistry Vol. 32; no. 12; pp. 3875 - 3890
• Main Authors: Tourné, Claude M., Tourné, Gilbert F., Malik, S.A., Weakley, T.J.R.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.01.1970
• ISSN: 0022-1902; 1878-1225
• DOI: 10.1016/0022-1902(70)80566-8

Triheteropolyanions XZW 11O 40H 2 n− ( x = B, Zn, P, Si, Ge; Z = Cu II , Mn II , Mn III ), XZMo 11O 40H 2 n− ( X = P, Si, Ge; Z = Mn II, Cu II), and X 2′CuW 17O 62H 2 8− ( X′ = P, As) are reported. All anions are degraded slowly by base; acid attack on the Cu II and Mn II anions is rapid, but the very stable free acids of the XMn III W 11O 40H 2 n− anions can be prepared. The molybdates are much less stable than the tungstates. The manganese complexes are high-spin; all salts are magnetically dilute. The Mn(II) complexes show metal-to-ligand charge-transfer bands in the near u.v. The Mn(III) 20,000 cm −1 ligand-field bands show structure which cannot be satisfactorily explained. The Mn(III)/Mn(II) redox potentials range from +0·43 V to +0·88 V.