A periodic walk: A series of first-row transition metal complexes with the pentadentate ligand PY5

Robertus J. M. Klein Gebbink, Robert T. Jonas, Christian R. Goldsmith, T. Daniel P. Stack

    Research output: Contribution to journalArticleAcademicpeer-review

    Abstract

    A series of transition metal complexes derived from the pentadentate ligand PY5, 2,6-(bis-(bis-2-pyridyl)-methoxymethane)pyridine, illustrates the intrinsic propensity of this ligand to complex metal ions. X-ray structural data are provided for six complexes (1-6) with cations of the general formula [MII(PY5)(Cl]+, where M = Mn, Fe, Co, Ni, Cu, Zn. In complexes 1-4 and 6, the metal ions are coordinated in a distorted-octahedral fashion; the four terminal pyridines of PY5 occupy the equatorial sites while the axial positions are occupied by the bridging pyridine of PY5 and a chloride anion. Major distortions from an ideal octahedral geometry arise from displacement of the metal atom from the equatorial plane toward the chloride ligand and from differences in pyridine-metal-pyridine bond angles. The series of complexes shows that M(II) ions are consistently accommodated in the ligand by displacement of the metal ion from the PY5 pocket, a tilting of the axial pyridine subunit, and nonsymmetrical pyridine subunit ligation in the equatorial plane. The displacement from the ligand pocket increases with the ionic radius of M(II). The axial pyridine tilt, however, is approximately the same for all complexes and appears to be independent of the electronic ground state of M(II). In complex 5, the Cu(II) ion is coordinated by only four of the five pyridine subunits of the ligand, resulting in a square-pyramidal complex. The overall structural similarity of 5 with the other complexes reflects the strong tendency of PY5 to enforce a distorted-octahedral coordination geometry. Complexes 1-6 are further characterized in terms of solution magnetic susceptibility, electrochemical behavior, and optical properties. These show the high-spin nature of the complexes and the anticipated stabilization of the divalent oxidation state.
    Original languageEnglish
    Pages (from-to)4633-4641
    Number of pages9
    JournalInorganic Chemistry
    Volume41
    Issue number18
    DOIs
    Publication statusPublished - 9 Sept 2002

    Keywords

    • 2,6 [bis(bis 2 pyridyl)methoxymethane]pyridine
    • cobalt
    • copper
    • iron
    • ligand
    • manganese
    • metal complex
    • nickel
    • organometallic compound
    • pyridine
    • pyridine derivative
    • unclassified drug
    • zinc
    • acceleration
    • article
    • chemical bond
    • chemical structure
    • chemistry
    • complex formation
    • conformation
    • electrochemical analysis
    • electron spin resonance
    • geometry
    • metal binding
    • nuclear magnetic resonance spectroscopy
    • oxidation
    • oxidation reduction reaction
    • polarimetry
    • structure analysis
    • synthesis
    • X ray crystallography

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