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  • Synthesis and redox properties of dinuclear rhodium(II) carboxylates with 2,6-Di-tert-butylphenol (cas 128-39-2) moieties
  • Add time:09/27/2019         Source:infona.pl

    By exploiting the peculiar reactivity of [Rh 2 (μ-O 2 CBu t ) 4 (H 2 O) 2 ] (1) the examples of dinuclear rhodium(II) carboxylates containing N-donor axial ligands (2, 3) [Rh 2 (μ-O 2 CBu t ) 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-cyanоphenol pendants studied by means of ESR method in solutions leads to the formation of phenoxyl radicals 3′ in dirhodium system. The ESR data show the interaction of the unpaired electron with ligand nuclei ( 1 H, 14 N) and 103 Rh. 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±1kJ/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.

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    Next: Synthesis and redox properties of novel ferrocenes with redox active 2,6-Di-tert-butylphenol (cas 128-39-2) fragments: The first example of 2,6-di-tert-butylphenoxyl radicals in ferrocene system)

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