Mono-, di- and polynuclear copper(II) compounds derived from N-butyldiethanolamine: structural features, magnetism and catalytic activity for the mild peroxidative oxidation of cyclohexaneElectronic supplementary information (ESI) available: Additional figures on magnetic susceptibility studies. CCDC reference numbers 696844–696847. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b813160k

Autor: Katrin R. Gruenwald, Alexander M. Kirillov, Matti Haukka, Joaquin Sanchiz, Armando J. L. Pombeiro
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Zdroj: Dalton Transactions: An International Journal of Inorganic Chemistry; Mar2009, Vol. 2009 Issue 12, p2109-2120, 12p
Abstrakt: The new mononuclear [Cu(Hbdea)2]·2Hdnba (1), dinuclear [Cu2(μ-Hbdea)2(N3)2] (2) and [Cu2(μ-Hbdea)2(pta)2]·2H2O (3), and 1D polymeric [Cu2(μ-Hbdea)2(μ-tpa)]n·2nH2O (4) copper(II) compounds have been prepared by self-assembly, in aqueous alkali medium and at ambient conditions, from Cu(II) acetate, N-butyldiethanolamine (H2bdea) and the corresponding auxiliary reagents, 3,5-dinitrobenzoic acid (Hdnba), sodium azide, p-toluic acid (Hpta) and terephthalic acid (H2tpa), respectively. They have been fully characterized by IR spectroscopy, FAB-MS+, elemental and single-crystal X-ray diffraction analyses, the latter also revealing intensive intermolecular hydrogen bonding in 2–4, resulting in the extension of the structural motifs and generation of tetrameric aggregates (in 2) and 1D (in 3) or 2D (in 4) supramolecular networks. All compounds constitute the first examples of Cu complexes derived from N-butyldiethanolamine, while 4represents also the first coordination polymer bearing this ligand. Magnetic susceptibility measurements reveal that compound 1follows the Curie-Weiss law, whereas 2–4follow the Bleaney-Bowers dinuclear model displaying antiferromagnetic coupling. Compounds 1–4act as valuable catalyst precursors for the mild peroxidative oxidation of cyclohexane, by aqueous H2O2in acidic MeCN medium, to cyclohexanol and cyclohexanone with overall yields up to 38%. The effects of various acid additives (promoters) have been studied, showing the preferable use of trifluoroacetic (TFA), nitric and hydrochloric acids. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index