Unprecedented [V₂O]⁶⁺ core of a centrosymmetric thiosemicarbazonato dimer: Spontaneous deoxygenation of oxovanadium(IV)

The complex cation [{V(daptsc)(MeOH)}₂(μ-O)]²⁺ [daptsc^2- = 2,6-diacetylpyridine bis(thiosemicarbazonate)] is the first crystallographically elucidated dimer to possess a [V₂O] ⁶⁺ core, the [V^IV-O-V^IV]⁶⁺ structural unit, formed by cleavage of the multiple bond in the oxo-cation VO²⁺, is linear with the oxo group residing on a crystallographic center of inversion, and the temperature dependence of the magnetic data of the dimer is consistent with weak antiferromagnetic coupling of the d ¹-d¹ centers.