Synthesis and redox properties of dinuclear rhodium(II) carboxylates with 2,6-di-tert-butylphenol moieties

By exploiting the peculiar reactivity of [Rh-2(mu-O2CBut)(4)(H2O)(2)] (1) the examples of dinuclear rhodium(II) carboxylates containing N-donor axial ligands (2, 3) [Rh-2(mu-O2CBut)(4)L-2] [where L = benzonitrile (2), 3,5-di-tert-butyl-4-hydroxybenzonitrile (3)] were synthesized and characterized by elemental analysis, IR, multinuclear NMR spectroscopy, MALDI-TOF mass spectrometry. It was found by X-ray diffraction that pairs of 3 in crystals are associated through H atoms of phenol groups to produce a dimer of dimers. The chemical oxidation of dirhodium complexes with 2,6-di-tert-butyl-4-cyanophenol pendants studied by means of ESR method in solutions leads to the formation of phenoxyl radicals 30 in dirhodium system. The ESR data show the interaction of the unpaired electron with ligand nuclei (H-1, N-14) and Rh-103. The stability of radical complexes with phenoxyl fragments in axial position is influenced by the temperature. The enthalpy of the 3' decomposition followed by the formation of cyanophenoxyl radical as 20 +/- 1 kJ/mol was estimated. Redox transformations in dirhodium system including both metal and axial ligands were investigated by electrochemistry. CV experiments confirm the assumption of the metal oxidation (Rh-II -> Rh-III) as the first step following by the oxidation of the ligand. (C) 2010 Published by Elsevier B.V.