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Nucleophilic ligand substitution in triply deprotonated tetrapeptide complexes of copper(II) and nickel(II) with 1,10-phenanthroline and 2,2-bipyridine

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Abstract

Ligand substitution of the triply deprotonated tetrapeptide ligand with bulky α-carbon substituents, in the tetrapeptide complexes of Cu(II) and Ni(II) by the bidentate ligands 2,2-bipyridine and 1,10-phenanthroline has been studied. The mechanism in the CuII(H-3A4)2− and the CuII(H-3F4)2− complexes shows a proton-assisted nucleophilic attack, and the CuII(H-3V4)2− shows both proton-assisted and direct equatorial nucleophilic attack by the bidentate ligands. A factor of ten decrease in the rate of substitution from CuII(H-3A4)2− to CuII(H-3V4)2−, and also CuII(H-3F4)2− is an indication of a steric hindrance on the substitution rate because of atom overcrowding due to the size of the α-carbon substituents in the CuII(H-3V4)2− and CuII(H-3F4)2− complexes. The substitution of the triply deprotonated tetrapeptide ligand in NiII(H-3A4)2− by 2,2-bipyridine and 1,10-phenanthroline shows a kinetic behaviour completely different to that of the Cu(II)-tetrapeptide complexes. Only a direct equatorial nucleophilic attack by the bidentate ligands has been observed.

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Authors and Affiliations

  1. Chemistry Department, University of the Free State, P.O. Box 339, Bloemfontein, 9300, Republic of South Africa

    C. Robert Dennis, Jannie C. Swarts & Ernie H. G. Langner

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  1. C. Robert Dennis
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  2. Jannie C. Swarts
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  3. Ernie H. G. Langner
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Correspondence to C. Robert Dennis.

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Dennis, C.R., Swarts, J.C. & Langner, E.H.G. Nucleophilic ligand substitution in triply deprotonated tetrapeptide complexes of copper(II) and nickel(II) with 1,10-phenanthroline and 2,2-bipyridine. Transit Met Chem 43, 387–395 (2018). https://doi.org/10.1007/s11243-018-0226-4

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  • DOI: https://doi.org/10.1007/s11243-018-0226-4

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