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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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.

作者简介

E. Rikhter

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

Novosibirsk, Russia; Novosibirsk, Russia

E. Vikulova

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

Email: lazorevka@mail.ru
Novosibirsk, Russia

T. Sukhikh

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

Novosibirsk, Russia

A. Strigunovskaya

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

Novosibirsk, Russia; Novosibirsk, Russia

N. Morozova

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

Novosibirsk, Russia

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