trans,trans-(tpy)(Cl)2OsII(N2)OsII(Cl)2(tpy) (2) has been prepared by reduction of trans-[OsVI(tpy)(Cl)2(N)]+ (1). The 1-electron oxidation of 2 gives trans,trans-[(tpy)(Cl)2OsIII(N2) OsII(Cl)2(tpy)]+ (3). OsIII−OsII/OsII−OsII and OsIII−OsIII/OsIII−OsII couples appear at +0.21 and +0.77 V vs SSCE in DMF 0.1 M in [N(n-Bu)4](PF6) (ΔE1/2 = 560 mV). An intense ν(N⋮N) stretch at 2012 cm-1 in 3 in CD3CN is consistent with the X-ray crystal structure (shown) in revealing localized OsIII and OsII oxidation states. This mixed-valence cation is at the transition between class II and II in the Robin−Day classification scheme.
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Demadis et al. (1997) studied this question.
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