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Correlations between the Structures of Binuclear Copper(II) Tetracarboxylates with 1,4-Dioxane and the Nature of Substituent R in the Carboxylate Anion

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Abstract

The dissolution of aqueous copper(II) acetate in coordinating bidentate 1,4-dioxane (reflux) affords anhydrous mononuclear complex Cu2(µ-OOCMe)4(dioxane)2 (I) (Cu…Cu 2.5781(3) Å). The crystal of complex I contains contacts of the α-H atom of the CH2 fragments of coordinated dioxane with the oxygen atom of the bridging anion with the formation of the 2D metal-organic framework (MOF). The anionic exchange reactions of the acetate bridges by pivalate or trifluoroacetate groups with the corresponding acids in boiling dioxane give 1D MOF {Cu2(µ-OOCR)4(dioxane)}n (R = tBu (II), Cu…Cu 2.5493(7) Å; CF3 (III), Cu…Cu 2.6391(12) Å) characterized by the step and linear geometry, respectively. A similar reaction of Cu2(µ-OOCMe)4(OH2)2 with HOOCCF3 but at room temperature in the presence of crude benzene affords mononuclear complex Cu(OOCCF3)2(OH2)3·2 dioxane (IV). Complexes I–IV are studied by elemental and X-ray diffraction analyses (CIF files CCDC nos. 2052618 (I), 2052619 (II), 2052620 (III), and 2052617 (IV)). The influence of the electronic and steric factors of substituents R on the compositions and structures of the mononuclear complexes and MOFs with 1,4-dioxane are discussed for the synthesized and known copper(II) tetracarboxylates.

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ACKNOWLEDGMENTS

The XRD and IR spectral studies of the complexes were carried out using the equipment of the Center for Collective Use of Physical Methods of Investigation at the Kurnakov Institute of General and Inorganic Chemistry (Russian Academy of Sciences) functioning in terms of the state assignment of the Kurnakov Institute of General and Inorganic Chemistry (Russian Academy of Sciences) in the area of basic research.

Funding

This work was supported by the state assignment of the Kurnakov Institute of General and Inorganic Chemistry (Russian Academy of Sciences) in the area of basic research.

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Authors and Affiliations

  1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119992, Moscow, Russia

    M. A. Uvarova & S. E. Nefedov

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  1. M. A. Uvarova
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  2. S. E. Nefedov
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Correspondence to S. E. Nefedov.

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To blessed memory of Teacher: to the 80th birthday of Prof. A.A. Pasynskii

Translated by E. Yablonskaya

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Uvarova, M.A., Nefedov, S.E. Correlations between the Structures of Binuclear Copper(II) Tetracarboxylates with 1,4-Dioxane and the Nature of Substituent R in the Carboxylate Anion. Russ J Coord Chem 47, 399–408 (2021). https://doi.org/10.1134/S1070328421060087

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