TY - JOUR

T1 - Structure and Properties of Magnesium Complexes with Bulky β-Diketones: 2,2,6,6-Tetramethylheptane-3,5-dione and Its Methoxy-Substituted Derivative

AU - Rikhter, E. A.

AU - Vikulova, E. S.

AU - Sukhikh, T. S.

AU - Strigunovskaya, A. V.

AU - Morozova, N. B.

N1 - The study of the complex with the Thd ligand was supported by the Russian Science Foundation (project no. 24-79-10272).

PY - 2025/7

Y1 - 2025/7

N2 - 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 (the Mg coordination number (C.N.) is 5, 6), but in I, three μ,κ2:1-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 associated with any significant structural rearrangement, but C.N. of the unsaturated metal center changes from 5 to 6. Thermogravimetric analysis showed that complex I is more volatile and low-melting than II.

AB - 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 (the Mg coordination number (C.N.) is 5, 6), but in I, three μ,κ2:1-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 associated with any significant structural rearrangement, but C.N. of the unsaturated metal center changes from 5 to 6. Thermogravimetric analysis showed that complex I is more volatile and low-melting than II.

KW - X-ray diffraction

KW - magnesium

KW - thermogravimetry

KW - volatile complex

KW - β-diketonate

KW - ЛЕТУЧИЙ КОМПЛЕКС

KW - МАГНИЙ

KW - β-ДИКЕТОНАТ

KW - PCA

KW - ТЕРМОГРАММЕТРИЯ

UR - https://www.scopus.com/pages/publications/105019392436

UR - https://www.elibrary.ru/item.asp?id=83051259

UR - https://www.elibrary.ru/item.asp?id=83015068

UR - https://www.mendeley.com/catalogue/bc6d91f7-152b-34f1-b5dc-675a7d9ee4e9/

U2 - 10.1134/S1070328425600408

DO - 10.1134/S1070328425600408

M3 - Article

VL - 51

SP - 615

EP - 627

JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

SN - 1070-3284

IS - 7

M1 - 8

ER -