Abstract
Successive reversible E° values for the redox couples [MF6]z/z–1(z= 0, –1, –2) where M = Ta, W, Re, Os and Nb, Mo, (Tc), Ru, detected by cyclic voltammetry in MeCN over a 6 V range, follow linear progressions related to central ion nuclear and electronic structure for d0→ d1, d1→ d2, and d2→ d3 while deviations observed for d3→ d4 and subsequent couples are attributable to spin-pairing effects; corresponding 4dn/n+1 and 5dn/n+1couples are almost uniformly separated by 1.0 V.
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