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Nickel(II) complexes of the macrocyclic ligand 5-nitromethyl-5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene containing a pendant nitro group

Transition Metal Chemistry volume 23, pages 165–167 (1998)Cite this article

Abstract

The reaction of MeNO2 in the presence of Et3N with the nickel(II) complex of C-meso-5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene gives the nickel(II) complex of the 5-nitromethyl derivative containing a pendant nitro group. The complex is octahedral with the nitro group coordinated to nickel(II) via the aci-nitro tautomer. Although the complex contains one water molecule, six-coordination occurs by interaction with a neighbouring CH NO2- group in a polymeric structure. Recrystallisation from aqueous ammonia gives a blue paramagnetic complex with lattice ammonia. Addition of HClO4 to the blue paramagnetic hydrate gives the orange-brown diperchlorate salt with a pendant nitro group. This salt displays a planar octahedral equilibrium in aqueous solution, NiL+2H2O NiL(H2O)2, with K=0.28 at 40degC. The thermodynamic parameters for this equilibrium are DeltaH=-59+2kJmol-1and DeltaS=-200+5JK-1mol-1. The nitro group can be reduced with Zn/HCl to give the amino derivative. The configurations of the complexes are considered and the spectroscopic results discussed.

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Authors and Affiliations

  1. School of Chemistry, University of St Andrews, St Andrews, UK

    Robert W. Hay & M. Tofazzal. H. Tarafder

  2. Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland

    Bohdan Korybut-Daszkiewicz

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  1. Robert W. Hay
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  2. M. Tofazzal. H. Tarafder
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  3. Bohdan Korybut-Daszkiewicz
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Hay, R.W., Tarafder, M.T.H. & Korybut-Daszkiewicz, B. Nickel(II) complexes of the macrocyclic ligand 5-nitromethyl-5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene containing a pendant nitro group. Transition Metal Chemistry 23, 165–167 (1998). https://doi.org/10.1023/A:1006903328044

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