Di- and Tri-nuclear V$^{III}$ and Cr$^{III}$ Complexes of Dipyridyltriazoles: Ligand Rearrangements, Mixed Valency and Ferromagnetic Coupling

The first dinuclear and trinuclear chromium(III) and dinuclear vanadium(III) complexes of N$^{4}$-R-substituted-3,5-di(2-pyridyl)-1,2,4-triazole (Rdpt) ligands have been prepared by solvothermal complexations under inert atmospheres, and characterized. The reactions of Cr$^{III}$ and V$^{III}$ with adpt (R = amino) resulted in deamination of the ligand and yielded the dinuclear doubly-triazolate bridged complexes [V$_{2}^{III}$(dpt$^{-}$)$_{2}$Cl$_{4}$] (1) and [Cr$_{2}^{III}$(dpt$^{-}$)$_{2}$Cl$_{4}$] (2). In the case of the Cr$^{III}$ complex 2 this bridging results in a rare example of ferromagnetic coupling for a dinuclear Cr$^{III}$ compound. DFT studies confirm that in 2 the ferromagnetic coupling pathways dominate over the antiferromagnetic pathways, whereas in 1 the reverse occurs, consistent with the observed overall antiferromagnetic coupling in that case. It was also found that the use of different additives in the reaction allows the nuclearity of the Cr$^{III}$ product to be manipulated, giving either the dinuclear system, or the first example of a trinuclear circular helicate for a Rdpt complex, [Cr$_{3}^{III}$(dpt)$_{3}$Cl$_{6}$]·1¾MeCN·¼DCM (3). ... mehrReaction of N$^{4}$-pydpt (R = 4-pyridyl) with V$^{III}$ led to an unusual shift of the pyridyl substituent from N$^{4}$ to N$^{1}$ of the triazole, forming the ligand isomer N$^{1}$-pydpt, and giving a dinuclear doubly-triazole bridged complex, [V$_{2}^{III}$(N$^{1}$-pydpt)$_{2}$Cl$_{6}$]·2MeCN (4). Reaction with Cr$^{III}$ results in loss of the 4-pyridyl ring and a mixture of the di- and trinuclear complexes, 2 and 3. Interestingly, partial oxidation of the V$^{III}$ in dinuclear complex 4 to vanadyl V$^{IV}$=O was identified by crystallographic analysis of partially oxidized single crystals, [(V$^{IV}$O)$_{0.84}$(V$^{III}$)$_{1.16}$(N$^{1}$-pydpt)$_{2}$Cl$_{5.16}$] 0.84H$_{2}$O 1.16MeCN (5).