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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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.

作者简介

D. Tereshchenko

Moscow State University

Email: tereschenko_den@mail.ru
119991, Moscow, Russia

M. Buzoverov

Moscow State University

Email: tereschenko_den@mail.ru
119991, Moscow, Russia

T. Glazunova

Moscow State University

Email: tereschenko_den@mail.ru
119991, Moscow, Russia

E. Lermontova

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: tereschenko_den@mail.ru
119991, Moscow, Russia

V. Goncharenko

Lebedev Physical Institute, Russian Academy of Sciences; Higher School of Economics

Email: tereschenko_den@mail.ru
119991, Moscow, Russia; 101000, Moscow, Russia

T. Shatalova

Moscow State University

Email: tereschenko_den@mail.ru
119991, Moscow, Russia

E. Khlopkina

Moscow State University

Email: tereschenko_den@mail.ru
119991, Moscow, Russia

I. Morozov

Moscow State University

编辑信件的主要联系方式.
Email: tereschenko_den@mail.ru
119991, Moscow, Russia

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版权所有 © Д.С. Терещенко, М.Е. Бузоверов, Т.Ю. Глазунова, Э.Х. Лермонтова, В.Е. Гончаренко, Т.Б. Шаталова, Е.В. Хлопкина, И.В. Морозов, 2023

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