Catalysis of carbon tetrachloride conversion by copper complexes with monoethanolamine immobilized on the surface of silicaстатья

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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.

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[1] Catalysis of carbon tetrachloride conversion by copper complexes with monoethanolamine immobilized on the surface of silica / V. V. Smirnov, I. G. Tarkhanova, A. I. Kokorin et al. // Kinetics and Catalysis. — 2005. — Vol. 46, no. 1. — P. 65–71. The catalytic properties of silica-immobilized copper complexes with monoethanolamine in reactions of CCl4 addition to 1-octene and combined metathesis of C-Cl and C-H bonds in the CCl4-decane system were studied. The catalytic activity was found to be an extremal function of metal concentration. The increase of activity during the addition of CCl4 to octene as the metal content was decreased to similar to 0.3 wt % can be explained by an increase in the fraction of mononuclear copper complexes of differing composition. Further changes in activity were due to the formation of metal complexes with various ligand environments. A comparison between EPR data and catalytic properties suggested that the most active catalysts contained a considerable number of divalent copper complexes with a coordination environment of four nitrogen atoms, which are more effective than oxygen at increasing electron density on copper ion; this facilitated the reduction of Cu(II) to Cu(I). The above complexes are unstable because the ligands are rigidly fixed on the surface and strained structures are formed. Ligands in the coordination sphere of the metal can be readily replaced by substrate molecules, which exhibit weak solvating power. [ DOI ]

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