Synthesis and Crystal Structure of a Tetranuclear Cubane-like Nickel（Ⅱ） Complex with 2-Hydroxymethyl-N-salicylideneaniline

The tetranuclear cubane-like complex, [NiL（EtOH）]4·0.5EtOH （1） with tridentate Schiff base ligand （H2L= 2-Hydroxymethyl-N-salicylideneaniline） has been synthesized and its crystal structure and spectroscopic properties have been studied. The complex consists of a tetranuclear （NiO）4 cubane core, of which four nickel（Ⅱ） ions are bridged by μ3-alkoxide group and each nickel（Ⅱ） ion is coordinated to three μ3-alkoxide oxygen atoms, one imino nitrogen atom and one phenoxide oxygen atom from Schiff base ligand, and further ligated by one EtOH molecule, completing a distorted octahedral geometry.

Synthesis and Characterization of Novel μ-Carbonato Tetranuclear Copper Complexes [(Pip)4nCu4X4(CO3)2] in Aprotic Media

In this work, novel oxidative coupling complexes, [(Pip)4nCu4X4(CO3)2] (n = 1 or 2, X = Cl or Br, Pip = piperidine), are synthesized from the reaction of well characterized Lewis base [(Pip)4nCu4X4O2] with carbon dioxide as a Lewis acid in CH2Cl2. These carbonato-derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH2Cl2or phNO2. Cryoscopic measurements support tetranuclear structure for all of them. Electronic spectra in the near infrared with high molecular absorptivity may be explained for tetranuclear cuban structure to fulfil 3 halo-ligands for each copper centre in [(Pip)4nCu4X4(CO3)2]. The EPR spectra for [(Pip)4nCu4X4(CO3)2] complexes are axial type of spectra (dx2-y2 G.S) suggesting elongated tetragonal distortion for all of them. Cyclic voltammograms for [(Pip)4nCu4X4(CO3)2] are irreversible in character. These tetranuclear carbonato complexes show catalytical activity. They initiate the oxidation of 2,6-dimethylphenol (DMP) to 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ).