Synthesis, magnetic behaviour, and X-ray structures of dinuclear copper complexes with multiple bridges. Efficient and selective catalysts for polymerization of 2,6-dimethylphenol

Abstract

The use of a potentially tridentate mono-anionic bridging ligand, 1,3-bis(3,5-dimethylpyrazol-1-yl)propan-2-ol (bdmpp-H), in assembling new dimeric copper complexes with interesting magnetic properties has been investigated. The reaction of copper hydroxide or copper acetate with phenyl phosphinic acid or diphenyl phosphinic acid in the presence of bdmpp-H produces the dinuclear complexes [Cu(bdmpp)(ppi)]₂ (1) and [Cu(bdmpp)(dppi-H)]₂(dppi)₂ (2) (ppi-H = phenylphosphinic acid; dppi-H = diphenylphosphinic acid), respectively. The products have been characterized with the help of analytical, thermal, and spectroscopic (IR, UV-vis, and EPR) techniques. Single crystal X-ray diffraction studies of 1 and 2 reveal that the two bdmpp ligands hold together the dimeric copper unit in each complex through µ-O alkoxide and the pyrazolyl nitrogen ligating centers. Two phenyl phosphinate ligands additionally bridge the dicopper core in 1 to result in octahedral coordination geometry around each metal ion. The diphenyl phosphinic acid acts as a terminal ligand in 2, and thus completes a square pyramidal geometry around each copper ion. Both complexes show a very short Cu⋯Cu separation (3.001 and 3.065 Å for 1 and 2, respectively). The investigation of the magnetic properties reveals the efficiency of the double alkoxide bridge between the two paramagnetic copper ions to mediate strong antiferromagnetic interactions [J/k_B = −620(5) K (−431(4) cm⁻¹) and −685(5) K (−476(4) cm⁻¹) for 1 and 2, respectively]. Compounds 1 and 2, along with a few other copper phosphate complexes, were tested as catalysts for the oxidative polymerization of 2,6-dimethylphenol; 1 and 2 were found to be efficient catalysts with an increased selectivity for the formation of the polyphenylene ether. However a related mononuclear octahedral copper complex [Cu(imz)₄(dtbp)₂] (dtbp-H = di-tert-butylphosphate) was found to be more efficient.