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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Authors: | G. A. Abakumov V. K. Cherkasov M. P. Bubnov L. G. Abakumova V. N. Ikorskii G. V. Romanenko A. I. Poddel’sky |
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Affiliation: | (1) G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603950 Nizhny Novgorod, Russian Federation;(2) International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090 Novosibirsk, Russian Federation |
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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). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 43–51, January, 2006. |
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Keywords: | cobalt iron manganese o-iminobenzoquinone o-iminobenzosemiquinone X-ray diffraction magnetochemistry |
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