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An unexpected mixed-valence cobalt(II)/cobalt(III) complex of a pyrrole-containing tridentate Schiff-base ligand

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Abstract

The synthesis and characterisation of an unexpected mixed-valence complex [CoIII(L1)(aep)(NCS)]2[CoII(NCS)4] 1, of the deprotonated tridentate Schiff-base ligand (L1)− [where HL1 is N-(1H-pyrrol-2-ylmethylene)-2-pyridineethanamine], is reported. This complex was synthesised by both non-stoichiometric and stoichiometric one pot procedures, by mixing 2-formylpyrrole, 2-(2-aminoethyl)pyridine (aep), cobalt(II) acetate and sodium thiocyanate at room temperature. The crystal structure of 1·Et2O confirmed that two, almost identical, mixed ligand octahedral cobalt(III) monocationic complexes crystallise with a tetrahedral cobalt(II) tetra-thiocyanato dianionic counter ion.

Graphical abstract

An unexpected mixed-valence complex [CoIII(L1)(aep)(NCS)]2[CoII(NCS)4] 1, of the deprotonated tridentate Schiff-base ligand (L1)−, was synthesised by both non-stoichiometric and stoichiometric one pot procedures. The crystal structure of 1·Et2O confirmed that two, almost identical, mixed ligand octahedral cobalt(III) monocationic complexes crystallise with a tetrahedral cobalt(II) tetra-thiocyanato dianionic counter ion.

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Acknowledgments

We are grateful to the University of Otago for the award of a Prestigious Postgraduate Scholarship (to RL) and for funding this research. We thank Dr. J. Wikaira and Professor W. T. Robinson (University of Canterbury) for the X-ray data collection. We are pleased to dedicate this paper to Professor Len Lindoy (University of Sydney) on the occasion of his 75th birthday and give him heartfelt thanks for all of the active support and encouragement he has given us over the years. Thanks heaps Len!

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  1. Rongqing Li

    Present address: Jiangsu Key Laboratory for the Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, 111 Changjiang Road-West, Huaiyin District, Huai’an, 223300, Jiangsu Province, People’s Republic of China

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  1. Department of Chemistry, MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, PO Box 56, Dunedin, 9054, New Zealand

    Rongqing Li & Sally Brooker

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  1. Rongqing Li
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  2. Sally Brooker
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Correspondence to Sally Brooker.

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This article is dedicated to Professor Len Lindoy on the occasion of his 75th birthday.

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Li, R., Brooker, S. An unexpected mixed-valence cobalt(II)/cobalt(III) complex of a pyrrole-containing tridentate Schiff-base ligand. J Incl Phenom Macrocycl Chem 71, 303–309 (2011). https://doi.org/10.1007/s10847-011-9977-7

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