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Rotational Correlation Times of Tris(acetylacetonato)cobalt(III) in Various Organic Solvents by NMR Relaxation Measurements

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Abstract

NMR relaxation times of the dual-specific nuclei of metal cobalt-59 and ligand methine carbon-13 for tris(2,4-pentanedionato)cobalt(III), which is commonly named as tris(acetylacetonato)cobalt(III), [Co(acac)3], in four organic solvents, acetonitrile, dichloromethane, chloroform, and benzene, have been measured at several temperatures. The rotational correlation times of complex molecules in different solvents, obtained from the NMR relaxation times, can be semi-quantitatively described by the hydrodynamic Debye–Einstein–Stokes (DES) model. However, the slight deviations from the DES model were observed dependent on the kind of solvents, where the effective rotational volume increased in the order of C6H6 ~ CH3CN < CH2Cl2 < CDCl3. In chloroform solution, where two solvent molecules are specifically bound to [Co(acac)3] in the ligands’ hollows, the complex molecule can rotate accompanying the chloroform molecules solvated and/or the friction in the outer coordination sphere can be increased by the specific interactions in view of the larger effective rotational volume. The present results indicate that the rotational dynamics of [Co(acac)3] in solution is quite sensitive to the solute–solvent interactions in the outer coordination sphere as well as the viscosity of solution.

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  1. Mitsuhiro Kanakubo

    Present address: National Institute of Advanced Industrial Science and Technology (AIST), 4-2-1Nigatake, Miyagino-Ku, Sendai, 983-8551, Japan

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyoda-Ku, Tokyo, 102-8554, Japan

    Mitsuhiro Kanakubo, Naoko Inoue, Haruko Ikeuchi & Gen P. Satô

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  1. Mitsuhiro Kanakubo
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  2. Naoko Inoue
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Contributions

Mitsuhirko Kanakubo contributed to conceptualization, analysis, investigation, methodology, validation, writing - original draft, review and editing, and visualization. Naoko Inoue contributed to analysis and investigation. Haruko Ikeuchi contributed to conceptualization, methodology, writing - review and editing, and supervision. Gen P. Satô contributed to conceptualization, methodology, writing - review and editing, and supervision.

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Correspondence to Mitsuhiro Kanakubo or Haruko Ikeuchi.

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Kanakubo, M., Inoue, N., Ikeuchi, H. et al. Rotational Correlation Times of Tris(acetylacetonato)cobalt(III) in Various Organic Solvents by NMR Relaxation Measurements. J Solution Chem 52, 1117–1128 (2023). https://doi.org/10.1007/s10953-023-01300-4

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