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Synthesis and Properties of Cobalt(III) Complexes of 4-Substituted Pyridine-Capped Dioxocyclams
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    Synthesis and Properties of Cobalt(III) Complexes of 4-Substituted Pyridine-Capped Dioxocyclams
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    Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2005, 44, 25, 9162–9174
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    https://doi.org/10.1021/ic050200h
    Published October 28, 2005
    Copyright © 2005 American Chemical Society

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    Cobalt(III) acetate and cyanide complexes of a series of 5,12-dioxocyclams capped across the 1,8-position by 4-substituted pyridines or pyrazine were synthesized and fully characterized. Both the spectroscopic and structural parameters for these complexes were remarkably insensitive to the electronic nature of the capping group, which ranged from the π-accepting pyrazine group to the σ-donating 4-[(dimethylamino)phenyl]pyridyl group. All of the complexes underwent an irreversible, one-electron reduction [Co(III) → Co(II)] at potentials ranging from −0.95 V vs saturated calomel electrode (SCE) for the pyrazine-capped cobalt acetate complex to −1.36 V vs SCE for the pyridine-capped cobalt cyanide complexes. Pyridine-capped cobalt(III) cyanide complex 6a underwent reaction with Rh2(OAc)4 and ruthenium(II) phthalocyanine[bis(benzonitrile)] to form tetrametallic (7) and trimetallic (8) complexes through coordination bridging by the cyanide nitrogen lone pair. These complexes represent two quite different structural types for cyanide-bridged polymetallics. Complex 7 has a relatively long (2.192 Å) cyanide N-to-Rh bond, and the C⋮NRh bond angle (157.6°) is strongly distorted from linear. In contrast, complex 8 has a substantially shortened cyanide N-to-Ru bond (2.017 Å) and an almost linear arrangement along the entire bridging axis of the molecule.

    Copyright © 2005 American Chemical Society

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     To whom correspondence should be addressed. E-mail: [email protected].

    Supporting Information Available

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    Tables of crystal data, structure solutions and refinement, atomic coordinates, bond lengths and angles, and anisotropic thermal parameters for 4a, 5a, 5b, 6a, 6b, 7, and 8, and CIF data. This material is available free of charge via the Internet at http://pubs.acs.org.

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    This article is cited by 13 publications.

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    8. Yifan Shi, Atta M. Arif, Richard D. Ernst. Use of pyrazolyl ligands for the formation of a bimetallic cobalt–ruthenium complex. Polyhedron 2011, 30 (11) , 1899-1905. https://doi.org/10.1016/j.poly.2011.04.023
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    11. Jörg Müller, Christian Würtele, Olaf Walter, Siegfried Schindler. Transformation of Nitrile to Cyanide and Aldehyde Using a Cobalt(II) Complex and Dioxygen. Angewandte Chemie International Edition 2007, 46 (41) , 7775-7777. https://doi.org/10.1002/anie.200701408
    12. Jörg Müller, Christian Würtele, Olaf Walter, Siegfried Schindler. Umwandlung eines Nitrils in Cyanid und Aldehyd unter Verwendung von Sauerstoff und einem Cobalt(II)‐Komplex. Angewandte Chemie 2007, 119 (41) , 7922-7924. https://doi.org/10.1002/ange.200701408
    13. Stephen J. Archibald. Macrocyclic coordination chemistry. Annual Reports Section "A" (Inorganic Chemistry) 2006, 102 , 332. https://doi.org/10.1039/b514842c

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2005, 44, 25, 9162–9174
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic050200h
    Published October 28, 2005
    Copyright © 2005 American Chemical Society

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