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Switchover from NiIIN2O2 to NiIIN2O2S2 coordination triggered by the redox behaviour of a non-innocent 2-aminophenolate ligand

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Abstract

Structural analysis of four-coordinate (S = 0) complex [Ni(L1)2] 1 (H2L1 = 4,6-di-tert-butyl-2-(2-benzylthiophenyl)aminophenol) revealed that it has approximately planar NiN2O2 coordination with dangling thioether arms (Mukherjee A and Mukherjee R 2005 Indian J Chem 50A 484–490). The two coordinated ligands are in 2-iminobenzosemiquinonate(1−) π radical (LISQ)·− redox level. Chemical oxidation of 1 by [Fe(η5-C5H5)2](PF6) in CH2Cl2 in the air led to oxidation of one of the (LISQ)·− ligands affording a six-coordinate Ni(II) complex [Ni(L1)2](PF6) 2 in mer configuration. The two tridentate ligands are in (LISQ)·− and 2-iminobenzoquinone (LIBQ)0 redox level (ligand mixed valency). The Ni–N/O/S distances and ligand backbone metrical parameters led us to assign unambiguously the electronic structure of 11+/2 as [NiII{(LISQ)·−}{(LIBQ)0}]1+. The EPR spectral signal of 2 at 120 K exhibits a very large g anisotropy and the magnetic measurement indicates an S = 3/2 ground state. The potential shift observed in going from 1 to coulometrically-generated 12+ is marginal. DFT calculations at the CAM-B3LYP level of theory rationalizes the electronic structure of 1, 11+ and 12+. Time-Dependent (TD)-DFT calculations throw light on the nature of observed absorptions of 1, 11+ and 12+.

Graphic abstract

One-electron oxidation of four-coordinate [NiII(L1)2] 1 (S = 0) Causes additional coordination by two dangling thioethers affording six-coordinate [NiII(L1)2](PF6) 2 (S = 3/2); characterization of 2 has been done by X-ray structural analysis, MOS values, magnetism (ferromagnetic coupling), absorption and EPR spectra, and DFT and TD-DFT calculations.

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Author notes

  1. Rabindranath Mukherjee

    Present address: Department of Chemistry, Indian Institute of Technology (Indian School of Mines) Dhanbad, Dhanbad, 826 004, India

Authors and Affiliations

  1. Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208 016, India

    Akram Ali, Arunava Sengupta & Rabindranath Mukherjee

  2. Department of Chemistry, CMP College, University of Allahabad, Prayagraj, 211 002, India

    Akram Ali

  3. Department of Chemistry, Techno India University, West Bengal, Kolkata, 700 091, India

    Arunava Sengupta

  4. Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMOL), Universitat de València, Polígono de la Coma, s/n, 46980, Paterna, València, Spain

    Francesc Lloret

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Correspondence to Rabindranath Mukherjee.

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Rabindranath Mukherjee: Dedicated to (late) Professor Bhaskar G Maiya.

Special Issue on Beyond Classical Chemistry

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Ali, A., Sengupta, A., Lloret, F. et al. Switchover from NiIIN2O2 to NiIIN2O2S2 coordination triggered by the redox behaviour of a non-innocent 2-aminophenolate ligand. J Chem Sci 133, 110 (2021). https://doi.org/10.1007/s12039-021-01961-y

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