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A New Family of Trinuclear Complexes (CH3)4N[M3(µ3-F)(TFA)6(py)3] (M = Mn, Co, Ni, Cu, Zn): Synthesis, Crystal Structure, and Thermal Stability

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Abstract

Trinuclear complexes Me4N[Ni3(µ3-F)(TFA)6(MeOH)2(H2O)] (1) and Me4N[M3(μ3-F)(TFA)6(py)3] (M = Mn (2), Co (3), Ni (4), Cu (5), Zn (6)) have been synthesized by crystallization from methanol solutions. Single-crystal X-ray diffraction shows that compounds 1–6 are composed of tetramethylammonium cations Me4N+ and trinuclear triangular anions [Ni3(µ3-F)(TFA)6(MeOH)2(H2O)]– (1) or [M3(μ3-F)(TFA)6(py)3]– (2–6) centered by the μ3-F atom. The bridging trifluoroacetate anions (TFA–) located along the triangle edges link pairs of M2+ cations, and the axial positions are occupied by MeOH, H2O, or pyridine (py) molecules. In 2, the pyridine molecules are nearly coplanar with the [M3F] triangle, while in the other structures they are turned almost perpendicularly. The different orientations of py molecules lead to different packing motifs: columns of alternating trinuclear anions and Me4N+ cations are formed in 2, while in 3–6 anions and cations form neutral layers. A significant role in the organization of structures 1–6 is played by non-covalent interactions, such as hydrogen bonds and stacking and CH···π interactions. Heating complexes 2–4 above 200°С turns out to lead to a stepwise thermal decomposition, which begins with the elimination of py and ends with the formation of d-metal fluoride above 300°С.

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ACKNOWLEDGMENTS

The authors are grateful to the Shared Facility Center “Polymer Research Center” of the Institute of Synthetic Polymer Materials, RAS, with the support of the Ministry of Science and Higher Education of the Russian Federation (subject no. 0071-2021-0004) for the opportunity to conduct thermogravimetric analysis. The work used equipment purchased at the expense of the Development Program of the Moscow State University.

Funding

The study was supported by the Russian Science Foundation (project no. 22-72-10034).

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Authors and Affiliations

  1. Moscow State University, 119991, Moscow, Russia

    D. S. Tereshchenko, M. E. Buzoverov, T. Yu. Glazunova, T. B. Shatalova, E. V. Khlopkina & I. V. Morozov

  2. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991, Moscow, Russia

    E. Kh. Lermontova

  3. Lebedev Physical Institute, Russian Academy of Sciences, 119991, Moscow, Russia

    V. E. Goncharenko

  4. Higher School of Economics, 101000, Moscow, Russia

    V. E. Goncharenko

Authors
  1. D. S. Tereshchenko
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  2. M. E. Buzoverov
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  3. T. Yu. Glazunova
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  4. E. Kh. Lermontova
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  5. V. E. Goncharenko
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  6. T. B. Shatalova
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  7. E. V. Khlopkina
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  8. I. V. Morozov
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Correspondence to D. S. Tereshchenko.

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Translated by G. Kirakosyan

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Tereshchenko, D.S., Buzoverov, M.E., Glazunova, T.Y. et al. A New Family of Trinuclear Complexes (CH3)4N[M3(µ3-F)(TFA)6(py)3] (M = Mn, Co, Ni, Cu, Zn): Synthesis, Crystal Structure, and Thermal Stability. Russ. J. Inorg. Chem. 68, 1282–1292 (2023). https://doi.org/10.1134/S0036023623601666

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