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Synthesis, structure, and electrochemistry of pyridinecarboxamide cobalt(III) complexes; the effect of bridge substituents on the redox properties

Lookup NU author(s): Professor Mohammad Habibi, Dr Ross Harrington, Emeritus Professor Bill Clegg

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Abstract

Two series of complexes of the types trans-[CoIII(Mebpb)(amine)2]ClO4 {Mebpb2- = N,N-bis(pyridine-2-carboxamido)-4-methylbenzene dianion, and amine = pyrrolidine (prldn) (1a), piperidine (pprdn) (2a), morpholine (mrpln) (3a), benzylamine (bzlan) (4a)}, and trans-[CoIII(cbpb)(amine)2]X {cbpb2- = N,N-bis(pyridine-2-carboxamido)-4-chlorobenzene dianion, and amine = pyrrolidine (prldn), X = PF6 (1b), piperidine (pprdn), X = PF6 (2b), morpholine (mrpln), X = ClO4 (3b), benzylamine (bzlan), X = PF6 (4b)} have been synthesized and characterized by elemental analyses, IR, UV-Vis, and 1H NMR spectroscopy. The crystal structure of 1a has been determined by X-ray diffraction. The electrochemical behavior of these complexes, with the goal of evaluating the effect of axial ligation and equatorial substitution on the redox properties, is also reported. The reduction potential of CoIII, ranging from -0.53 V for (1a) to -0.31 V for (3a) and from -0.48 V for (1b) to -0.22 V for (3b) show a relatively good correlation with the σ-donor ability of the axial ligands. The methyl and chloro substituents of the equatorial ligand have a considerable effect on the redox potentials of the central cobalt ion and the ligand-centered redox processes. © 2008 Elsevier Ltd. All rights reserved.


Publication metadata

Author(s): Meghdadi S, Amirnasr M, Habibi MH, Amiri A, Ghodsi V, Rohani A, Harrington RW, Clegg W

Publication type: Article

Publication status: Published

Journal: Polyhedron

Year: 2008

Volume: 27

Issue: 13

Pages: 2771-2778

ISSN (print): 0277-5387

ISSN (electronic): 1873-3719

Publisher: Pergamon

URL: http://dx.doi.org/10.1016/j.poly.2008.05.031

DOI: 10.1016/j.poly.2008.05.031


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