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

D. S. Tereshchenko; Терещенко Д. С.; M. E. Buzoverov; Бузоверов М. Е.; T. Yu. Glazunova; Глазунова Т. Ю.; E. Kh. Lermontova; Лермонтова Э. Х.; V. E. Goncharenko; Гончаренко В. Е.; T. B. Shatalova; Шаталова Т. Б.; E. V. Khlopkina; Хлопкина Е. В.; I. V. Morozov; Морозов И. В.

doi:10.31857/S0044457X23601190

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

Authors: Tereshchenko D.S.¹, Buzoverov M.E.¹, Glazunova T.Y.¹, Lermontova E.K.², Goncharenko V.E.³^,4, Shatalova T.B.¹, Khlopkina E.V.¹, Morozov I.V.¹
Affiliations:
1. Moscow State University
2. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
3. Lebedev Physical Institute, Russian Academy of Sciences
4. Higher School of Economics
Issue: Vol 68, No 9 (2023)
Pages: 1312-1323
Section: КООРДИНАЦИОННЫЕ СОЕДИНЕНИЯ
URL: https://rjmseer.com/0044-457X/article/view/666286
DOI: https://doi.org/10.31857/S0044457X23601190
EDN: https://elibrary.ru/WLAQTQ
ID: 666286

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Abstract
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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.

Keywords

triangular fluorocarboxylates, transition metal trifluoroacetate complexes

References

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