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Synthesis and structures of five-coordinate bis-o-iminobenzosemiquinone complexes M(ISQ-R)2X (X = Cl, Br, I, or SCN; M = CoIII, FeIII, or MnIII)

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Abstract

New five-coordinate complexes Co(ISQ-Pri)2Cl, Co(ISQ-Me)2Cl, Co(ISQ-Me)2I, Co(ISQ-Me)2(SCN), Mn(ISQ-Pri)2Cl, and Fe(ISQ-Me)2Br (ISQ-Pri and ISQ-Me are the 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-and 4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-iminobenzosemiquinone radical anions, respectively) were synthesized. The complexes were characterized by UV-Vis and IR spectroscopy and magnetochemistry. The molecular structures of the Fe(ISQ-Me)2Br and Mn(ISQ-Pri)2Cl complexes were established by X-ray diffraction. The singlet ground state (S = 0) of the cobalt complexes is caused by antiferromagnetic coupling between the unpaired electrons of the radical ligands (S = 1/2) through the fully occupied atomic orbitals of low-spin cobalt(III) (d6, S = 0). The effective magnetic moments of the complexes at 10 K are 0.18 μB for Co(ISQ-Pri)2Cl and 0.16 μB for Co(ISQ-Me)2I. The ground state of the manganese complex is triplet (S = 1). Two unpaired electrons of the o-iminobenzosemiquinone ligands are strongly antiferromagnetically coupled with two of four unpaired electrons of high-spin manganese(III) (d4, S = 2).

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Authors and Affiliations

  1. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603950, Nizhny Novgorod, Russian Federation

    G. A. Abakumov, V. K. Cherkasov, M. P. Bubnov, L. G. Abakumova & A. I. Poddel’sky

  2. International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090, Novosibirsk, Russian Federation

    V. N. Ikorskii & G. V. Romanenko

Authors
  1. G. A. Abakumov
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  2. V. K. Cherkasov
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  3. M. P. Bubnov
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  4. L. G. Abakumova
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  5. V. N. Ikorskii
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  6. G. V. Romanenko
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  7. A. I. Poddel’sky
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 43–51, January, 2006.

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Abakumov, G.A., Cherkasov, V.K., Bubnov, M.P. et al. Synthesis and structures of five-coordinate bis-o-iminobenzosemiquinone complexes M(ISQ-R)2X (X = Cl, Br, I, or SCN; M = CoIII, FeIII, or MnIII). Russ Chem Bull 55, 44–52 (2006). https://doi.org/10.1007/s11172-006-0213-3

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  • DOI: https://doi.org/10.1007/s11172-006-0213-3

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