Embracing ligands. Synthesis, characterisation and the correlation between 59Co NMR and ligand field parameters of Co(III) complexes with a new class of nitrogen-thioether multidentate ligand

Clint A. Sharrad, Germán E. Cavigliasso, Robert Stranger, Lawrence R. Gahan*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    6 Citations (Scopus)

    Abstract

    The syntheses of the hexadentate ligands 2,2,10,10-tetra(methyleneamine)-4,8-dithiaundecane (PrN4S2amp), 2,2,11,11-tetra(methyleneamine)-4,9-dithiadodecane (BuN4S2amp), and 1,2-bis(4,4-methyleneamine)-2-thiapentyl)benzene (XyN4S2amp) are reported and the complexes [Co(RN4S2amp)]3+ (R = Pr, Bu, Xy) characterised by single crystal X-ray study. The low-temperature (11 K) absorption spectra have been measured in Nafion films. From the observed positions of both spin-allowed 1A1g1T1g and 1A1g1T2g and spin forbidden 1A1g3T1g and 1A1g3T2g bands, octahedral ligand-field parameters (10Dq, B and C) have been determined. DFT calculations suggest that significant interaction between the d-d and CT excitations occurs for the complexes. The calculations offer an explanation for the observed deviations from linearity of the relationship between 59Co magnetogyric ratio and β(ΔE)-1 (β = the nephelauxetic ratio; ΔE the energy of the 1A1g1T1g transition) for a series of amine and mixed amine/thioether donor complexes.

    Original languageEnglish
    Pages (from-to)767-777
    Number of pages11
    JournalDalton Transactions
    Issue number5
    DOIs
    Publication statusPublished - 7 Mar 2004

    Fingerprint

    Dive into the research topics of 'Embracing ligands. Synthesis, characterisation and the correlation between 59Co NMR and ligand field parameters of Co(III) complexes with a new class of nitrogen-thioether multidentate ligand'. Together they form a unique fingerprint.

    Cite this