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|標題:||Crystal of meso-p-tolyl-porphyrinato copper(II) Cu(tptp) and di-cation ion-pair complex H(4)tptp (2+) CF3SO3 (2)(-) formation during the reaction of Cu(CF3SO3)(2) with meso-p-tolyl-porphyrin in CDCl3||作者:||Tsai, C.H.
|關鍵字:||crystal structures;Cu2+ porphyrin complexes;protonated porphyrins;SAT;complexes;electron spin resonance;nuclear magnetic resonance;magnetic-resonance spectroscopy;sitting-atop complex;5,10,15,20-tetraphenylporphyrin;tolylporphyrin;acetonitrile;oxidation;kinetics||Project:||Polyhedron||期刊/報告no：:||Polyhedron, Volume 19, Issue 6, Page(s) 633-639.||摘要:||
In the NMR and ESR time-scale of this experiment, an attempt was made to prepare the copper sitting-atop (SAT) species [ Cu(H(2)tptp)](2+) by the reaction of Cu(CF3SO3)(2) with meso-p-tolyl-porphyrin (H(2)tptp) in CDCl3; however, this led to the formation of meso-p-tolylporphyrinatocopper(II) Cu(tptp) and the protonated porphyrin [H(4)tptp](2+) [CF3SO3](2)(-) (2a). Previous researchers might have misinterpreted the SAT [Cu(H(2)tpp)](2+) complex as being a single component instead of a mixture of [H(4)tpp](2+) [CF3SO3](2)(-) (1) and Cu(tpp) for a similar reaction between 5,10,15,20-tetraphenylporphyrin H(2)tpp and Cu(CF3SO3)(2) in CH3CN. This work determines the crystal structure of Cu(tptp) and its hyperfine constants a(Cu) = 94.0 G and a(N) = 15.8 G using ESR. The crystal structure of [H(4)tptp](2+) [CH3SO3](2)(-) (3) is reported and employed to simulate the groupings of [H(4)tptp](2+) and CF3SO3- in the di-cation ion-pair complex 2a. (C) 2000 Elsevier Science Ltd All rights reserved.
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