Reaction Kinetics, Mechanisms and Catalysis
Volume/Issue:
Volume 107: Issue 1
Proton-transfer reactions of copper(II)- and nickel(II) tetrapeptide complexes with bulky α-carbon substituents
Authors:
C. Robert Dennis Chemistry Department, University of the Free State, P.O. Box 339, Bloemfontein 9300, Republic of South Africa

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

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Dale W. Margerum Prof. Emeritus Inorganic and Analytical Chemistry, Purdue University, West Lafayette, IN, 9307, USA

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Pages:
27–38
Online Publication Date:
28 Jun 2012
Publication Date:
01 Oct 2012
Article Category:
Research Article
DOI:
https://doi.org/10.1007/s11144-012-0467-8
Keywords:
Kinetics; Peptide complex; Protonation; Aqeuos medium
Restricted access

Abstract

Protonation of copper(II)- and nickel(II) tetrapeptide complexes with bulky α-carbon substituents has been studied. The pKa-values for the second and terminal metal–N(peptide) bond formation have been determined spectrophotometrically. More than one deprotonated peptide nitrogen exists in a complex but the individual protonation steps for the different CuII–N(tetrapeptide) positions could not be accounted for by the variation of the hydrogen ion concentration in the same experiment, as the protonation of the different metal–N(tetrapeptide) positions takes place at different wavelengths. For the NiII-tetra-alanine complex, the proton transfer to the terminal and second deprotonated peptide nitrogens have been detected by varying the hydrogen ion at the same wavelength. The proton transfer to the terminal metal–N(tetrapeptide) of CuII- and NiII-tetrapeptide complexes show first order kinetics with respect to the hydrogen ion and the peptide complex concentration and proceed via an outside protonation pathway. The relatively high pKa values for the terminal deprotonated peptide nitrogen indicate the instability of this metal–N(peptide) bond due to strain in the chelate ring because of atom overcrowding of the bulky α-carbon substituents.

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Cover Reaction Kinetics, Mechanisms and Catalysis
Reaction Kinetics, Mechanisms and Catalysis
Print ISSN:
1878-5190
Online ISSN:
1878-5204

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Reaction Kinetics, Mechanisms and Catalysis
Language English
Size B5
Year of
Foundation		 1974
Volumes
per Year		 1
Issues
per Year		 6
Founder Akadémiai Kiadó
Founder's
Address		 H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address		 H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Responsible
Publisher		 Chief Executive Officer, Akadémiai Kiadó
ISSN 1878-5190 (Print)
ISSN 1878-5204 (Online)

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