Dimeric Oxidovanadium(IV) Complex Bearing 1,10-Phenanthroline
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TRUCTURE OF ORGANIC COMPOUNDS
Dimeric Oxidovanadium(IV) Complex Bearing 1,10-Phenanthroline I. Charamzováa,*, J. Honzíčeka, P. Kalendaa, J. Vinklárekb, and I. Císařovác a
Institute of Chemistry and Technology of Macromolecular Materials, Faculty of Chemical Technology, University of Pardubice, Pardubice, 53210 Czech Republic b Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Pardubice, 53210 Czech Republic c Department of Inorganic Chemistry, Faculty of Science, Charles University, Prague, CZ-12840 Czech Republic *e-mail: [email protected], [email protected] Received September 16, 2019; revised December 10, 2019; accepted March 16, 2020
Abstract—New crystals of di-μ-methoxido-bis[(2-ethylhexanoato-κO)oxido(1,10-phenanthrolineκ2N,N')vanadium(IV)], C42H52N4O8V2, have been synthesized, characterized by elemental analysis, infrared spectroscopy, electron paramagnetic resonance and X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P21/c: a = 13.0656(11) Å, b = 9.1474(8) Å, c = 17.0299(14) Å, β = 94.387(4)°, Z = 2, Rgt = 0.0617, wR(F2) = 0.169, T = 150(2) K. The dimeric oxidovanadium(IV) complex consists of two [VIVO(OCOC7H15)(phen)] units connected with two methanolate bridges. The vanadium atoms have a distorted octahedral environment with four oxygen and two nitrogen atoms. The V=O bond length is 1.601(3) Å; the V–O bond lengths in the symmetrical V2O2 core are 1.973(2) and 2.007(3) Å. The vanadium–oxygen bond lengths in the carboxylate are 1.974(3) Å. The V–N interatomic distances depend on the configuration towards the oxidoligand. Preliminary experiments on solvent-borne alkyd resins revealed promising catalytic activity in the auto-oxidation process. DOI: 10.1134/S1063774520070056
INTRODUCTION Alkyd resins, as saturated polyesters modified with unsaturated fatty acids, are spontaneously auto-oxidatively crosslinked polymers. However, the auto-oxidation process is very slow without the addition of dryers [1]. It is well known, that transition metal complexes are widely used for their ability to undergo redox changes necessary to accelerate the formation of alkyd resin films [2, 3]. Recognized studies report toxic and genotoxic properties of cobalt(II) compounds [4, 5], whereby cobalt(II) 2-ethylhexanoate is the most widely used dryer. In recent studies, oxidovanadium(IV) complexes [6, 7], along with complexes containing manganese [8] and iron [9], have been found to be powerful alkyd dryers and can serve as a possible replacement for cobalt(II) compounds. In this work, a new binuclear oxidovanadium(IV) complex containing methanolate bridges was synthetized and its catalytic activity in the auto-oxidation process was studied. Structure of the title compound was determined by single-crystal X-ray diffraction analysis.
EXPERIMENTAL Synthesis The binuclear oxidovanadium(IV) complex was prepared under nitrogen, 2-ethylhexanoic acid (1.9 mL, 12.0 mmol) and 1,10-phenanthroline (0.356 g, 2.0 mmol) were added to mi
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