Ferrocenylpyrazole—A versatile building block for hydrogen-bonded organometallic supramolecular assemblies |
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Authors: | Tomoyuki Mochida Fumiko Shimizu Kazuya Okazawa Daisuke Kuwahara |
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Institution: | a Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan b Research Center for Materials with Integrated Properties, c/o Faculty of Science, Toho University, Japan c The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan |
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Abstract: | The crystal architectures of 5-ferrocenylpyrazole (1) and its metal complexes were investigated. Compound 1 can form non-solvated and chloroform-solvated crystals. In both cases, 1 forms a zigzag one-dimensional architecture via NH?N hydrogen bonds. The hydrogen bond exhibits a twofold disorder, which was shown to be static by solid-state 13C NMR. In the solvated crystal, the chloroform is released at 415 K, associated with melting of the crystal. The reaction of 1 with metal salts provided metal-centered ferrocenyl clusters Zn(NO3)2(1)4] (4), Co(NO3)2(1)4] (5), CoCl2(1)4] (6), Zn(NCS)2(1)2] (7), cis-Pt(NH3)2(1)2](PF6)2 (8), and trans-Pt(NH3)2(1)4](PF6)2 (9). In all of these complexes, 1 acts as a monodentate ligand. In 4, 5, and 7, the multinuclear units are joined via hydrogen bonds to form supramolecular chains. Two polymorphs were found for the crystals of 4. Both are composed of the same hydrogen-bonded chains, but their arrangements are different. 5-Ferrocenyl-1-tritylpyrazole (2) and 4-ferrocenyl-1-methylpyrazole (3) were also crystallographically characterized. |
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Keywords: | Crystal structure Hydrogen bond Pyrazole Ferrocene Metal complex |
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