The first tridecanuclear nickel(II) cluster: [Ni13(OH)6(O2CMe)8(btaO)12(H2O)6(nPrOH)4] (btaOH = 1-hydroxybenzotriazole)

The reaction of 1-hydroxybenzotriazole (btaOH) with Ni(O2CMe)4 · 4H2O in nPrOH has led to the [Ni13(OH)6(O2CMe)8(btaO)12(H2O)6(nPrOH)4] (1) cluster; compound 1 is the first structurally characterized tridecanuclear nickel(II) cluster and the biggest metal/btaOH or btaO− cluster discovered to date. The centrosymmetric molecule contains the {Ni13(μ3-OH)6(μ3-ONNNR)12}8+ core (R– = C6H4–) and is characterized by competitive antiferromagnetic exchange interactions within its pentanuclear subunits containing the μ3-OH− bridges. The reaction of 1 with an excess of N3- ions in refluxing MeOH has led to the azido-bridged product [Ni13(N3)6(O2CMe)8(btaO)12(MeOH)10] (2).

The 1:1 Ni(O2CMe)2·4H2O/1-hydroxybenzotriazole reaction system in propanol gives a tridecanuclear cluster which has the shown {Ni13(μ3-OH)6(μ3-ONNNR)12}8+ core; the compound is the biggest metal 1-hydroxybenzotriazole cluster discovered to date and the first Ni13 complex. The μ3-OH− groups can be replaced by end-on, triply bridging N3- ligands.Figure optionsDownload as PowerPoint slide