Cu(II) complexes as catalyst precursors in the process of selective hydrogenation of diene hydrocarbons. (15th January 2023)

• Record Type: Journal Article
• Authors: Koshenskova, Kseniya A.; Lutsenko, Irina A.; Nebykov, Denis N.; Mokhov, Vladimir M.; Nelyubina, Yulia V.; Primakov, Petr V.; Popov, Yuri V.; Khoroshilov, Andrey V.; Kottsov, Sergey Yu.; Kiskin, Mikhail A.; Eremenko, Igor L.
• Is Part Of: Polyhedron. Volume 230(2023)
• Publication Date: 2023-01-15
• Subjects: Furancarboxylate copper(II) complexes -- Crystal structure -- Heterogeneous catalysis -- Copper nanoparticles -- Selective hydrogenation -- Simultaneous thermal analysis; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2022.116208
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Two new copper complexes with anions derived from 3-furancarboxylic/ 5-nitro-2-furancarboxylic acid and 4-phenylpyridine were obtained. These catalysts are the first example of copper catalysts for the selective hydrogenation of dicyclopentadiene in flow type reactors. Abstract: The reaction of copper(II) acetate with 3-furancarboxylic acid (Hfur) and 5-nitro-2-furancarboxylic acid (Hnfur) with participation of 4-phenylpyridine (phpy) in acetonitrile resulted in mononuclear complexes [Cu(L)2 (phpy)2 (H2 O)]·solv (L = fur (1 ), nfur (2 ); solv = phpy (1 )) whose structures were determined by direct single crystal X-ray analysis. According to X-ray data, the complexing component in 1 and 2 is in a distorted square-pyramidal environment (CuN2 O3 ); the pyramid base is formed by monodentate-bound oxygen atoms of fur - /nfur - anions and a pair of nitrogen atoms of the phpy moieties, while the water molecule occupies an axial position. It was found for the first time that copper nanoparticles immobilized on the surface of γ-Al2 O3 obtained by chemical reduction of 1 and 2 (pre-deposited on the surface from solution) with sodium tetrahydroborate show high selectivity of monohydrogenation of tricyclo[5.2.1.0 2, 6 ]deca-3, 8-diene (dicyclopentadiene, DCPD) to give tricyclo[5.2.1.0 2, 6 ]dec-4-ene (5, 6-dihydrocyclopentadiene, DHDCPD). The catalytic activity tests show high selectivity (up to 100 %) of the catalysts studied in the reaction of partial hydrogenation to DHDCPD under continuous process conditions even at high conversion values (up to 96 %) and with hydrogen present in excess. Thermal behavior of 1 and 2 was studied by simultaneous thermal analysis (STA).