Valence tautomerism induced nucleophilic ipso substitution in a coordinated tetrabromocatecholate ligand and diverse catalytic activity mimicking the function of phenoxazinone synthase


Two new manganese(III) complexes, [pyH][Mn(Br(4)Cat)(2)(PY)1 (1) and [Mn(Br(4)Cat)(Br(3)PYCat)(PY)(2)] (2), where py is pyridine, Br(4)CatH(2) is tetrabromocatechol and Br(3)pyCatH(2) is 3,5,6-tribromo-4-pyridiniumcatechol, derived from redox 'noninnocent' bromo-substituted catecholate ligands are reported. Both complexes were characterized by various spectroscopic techniques in addition to the single crystal X-ray crystallography, and the electrochemical behavior of these complexes was investigated by cyclic voltammetry. Variable temperature UV-vis spectral studies for complex I reveal an unprecedented observation in which a dramatic increase of the ligand-to-metal charge transfer band at 592 nm associated with concomitant change in color of the solution from olive-green to dark-green is noticed with increase in temperature. This unprecedented spectral feature is consistent with the formation of a new species 2 in which valence tautomerism induced aromatic nucleophilic substitution of a tetrabromocatecholate ligand by pyridine is observed. DFT calculations have been used to rationalize this unexpected result. To the best of our knowledge, the nucleophilic aromatic substitution of tetra-bromosemiquinone by pyridine to generate this pyridinium-containing catecholate ligand is the first example of valence tautomerism induced nucleophilic ipso substitution by a nitrogen containing ligand. Although the electrochemical behavior of both complexes is similar, the probable role of a positive charge on the ligand backbone has been discussed in order to justify the significantly higher catalytic activity of complex 2 over complex 1. (C) 2015 Elsevier B.V. All rights reserved.



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Panja, A; Jana, NC; Patra, M; Brandao, P; Moore, CE; Eichhorn, DM; Frontera, A

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A.P. would like to thank the Department of Science and Technology (DST), New Delhi, under FAST Track Scheme (Order No. SB/FT/CS-016/2012, dated 20/12/2013) for financial support. The authors thank the IISER, Kolkata for providing the EPR facility. The authors also thank Dr. J. P. Naskar, Department of Chemistry, Jadavpur University for the cyclic voltammetry experiment. A.F. thanks the DGICYT of Spain (projects CTQ2014-57393-C2-1-P and CONSOLIDER INGENIO 2010CSD2010-00065, FEDER funds).

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