Structure and properties of magnesium complexes with bulky β-diketones: 2,2,6,6-tetramethylheptane-3,5-dione and its methoxy-substituted derivative

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Abstract

In order to study the effect of bulky terminal substituents in the β-diketonate ligand on the structure and properties of volatile magnesium compounds, complexes with 2,2,6,6-tetramethylheptane-3,5-dione (HThd) and, for the first time, with 2-methoxy-2,6,6-trimethylheptane-3,5-dione (HZis) were obtained. The complexes [Mg2(L)4] (L = Thd (I), Zis (II)), the synthesis intermediates [Mg(H2O)2(L)2] (L = Thd (III), Zis (IV)), and aqua derivative [Mg2(H2O)(Zis)4] (V) were characterized by elemental analysis and IR spectroscopy. The structures of binuclear complexes and the synthesis by-product [Mg7(Zis)6(μ-OH)6]Cl2·5CHCl3 (VI) were established by X-ray diffraction (CCDC nos. 2424128 (Ia, a new polymorph), 2424130 (II), 2424129 (V), 2424126 (V · 1/2CHCl3), 2424127 (VI)). Both [Mg2(L)4] molecules are characterized by asymmetric environment of metal centers (Mg C.N. is 5, 6), but in I, three μ,κ2:κ1-ligands occupy bridging positions, while in II, two ligands have different coordinations (μ,κ2:κ1 and μ,κ2(O,O′):κ2(O′,OOMe)). The inclusion of water in II to give V is not accompanied by a considerable rearrangement of the structure, but C.N. of the unsaturated metal center changes from 5 to 6. It was shown by thermogravimetry that complex I is more volatile and low-melting than II.

About the authors

E. A. Rikhter

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences; Novosibirsk National Research State University

Novosibirsk, Russia; Novosibirsk, Russia

E. S. Vikulova

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: lazorevka@mail.ru
Novosibirsk, Russia

T. S. Sukhikh

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Novosibirsk, Russia

A. V. Strigunovskaya

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences; Novosibirsk National Research State University

Novosibirsk, Russia; Novosibirsk, Russia

N. B. Morozova

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Novosibirsk, Russia

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