Syntheses, structures, and properties of Co(III) complexes derived from polypyridine ligands containing one carboxamido nitrogen donor

Afshar, Raman K., Bhalla, Rajiv, Rowland, John M., Olmstead, Marilyn M. and Mascharak, Pradip K. (2006) Syntheses, structures, and properties of Co(III) complexes derived from polypyridine ligands containing one carboxamido nitrogen donor. Inorganica Chimica Acta, 359 12: 4105-4113. doi:10.1016/j.ica.2006.04.020


Author Afshar, Raman K.
Bhalla, Rajiv
Rowland, John M.
Olmstead, Marilyn M.
Mascharak, Pradip K.
Title Syntheses, structures, and properties of Co(III) complexes derived from polypyridine ligands containing one carboxamido nitrogen donor
Journal name Inorganica Chimica Acta   Check publisher's open access policy
ISSN 0020-1693
Publication date 2006-09-01
Sub-type Article (original research)
DOI 10.1016/j.ica.2006.04.020
Volume 359
Issue 12
Start page 4105
End page 4113
Total pages 9
Language eng
Subject 1303 Specialist Studies in Education
1604 Human Geography
1606 Political Science
2505 Materials Chemistry
Abstract Four cobalt(III) complexes containing the polypyridine pentadentate ligands N,N-bis(2-pyridylmethyl)amine-N′-ethyl-2-pyridine-2-carboxamide (PaPy3H), N,N-bis(2-pyridylmethyl)amine-N′-[1-(2-pyridylethyl)acetamide (MePcPy3H), and N,N-bis(2-pyridylmethyl)amine-N′-(2-pyridylmethyl)acetamide (PcPy3H), have been synthesized. All three ligands bind the Co(III) center in the same fashion with the exception of loss of conjugation between the carboxamide moiety and the pyridine ring in the latter two. The structures of [(PaPy3)Co(OH)][(PaPy3)Co(H2O)](ClO4)3 · 3H2O (1), [(PaPy3)Co(NO2)](ClO4) · 2MeCN (2), [(MePcPy3)Co(MeCN)](ClO4)2 · 0.5MeCN (3), and [(PcPy3)Co(Cl)](ClO4) · 2MeCN (4) have been determined. These ligands with strong-field carboxamido N donor stabilize the +3 oxidation state of the Co center as demonstrated by the facile oxidation of the corresponding Co(II) complexes (prepared in situ) by H2O2, [Fe(Cp)2](BF4), or nitric oxide (NO). The Co-Namido bond distances of 1-4 lie in the narrow range of 1.853-1.898 Å. 1H NMR spectra of these complexes confirm the low-spin d6 ground states of the metal centers.
Keyword Carboxamide group
Co(III) complexes
Nitric oxide
Pentadentate polypyridine ligands
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
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