caa a22 4500 467954151 CHVBK 20180405193745.0 cr unu---uuuuu 170328e20050101xx s 000 0 eng 10.1007/PL00021987 doi (NATIONALLICENCE)springer-10.1007/PL00021987 (NATIONALLICENCE)springer-10.1007/s10975-005-0045-4 Catalysis of carbon tetrachloride conversion by copper complexes with monoethanolamine immobilized on the surface of silica [Elektronische Daten] [V. Smirnov, I. Tarkhanova, A. Kokorin, V. Pergushov, D. Tsvetkov] 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 ~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. MAIK "Nauka/Interperiodica”, 2005 Smirnov V. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut Tarkhanova I. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut Kokorin A. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut Pergushov V. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut Tsvetkov D. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 65-71 0023-1584 46:1<65 2005 46 10975 https://doi.org/10.1007/PL00021987 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/PL00021987 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Smirnov V. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut NATIONALLICENCE 700 1- Tarkhanova I. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut NATIONALLICENCE 700 1- Kokorin A. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut NATIONALLICENCE 700 1- Pergushov V. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut NATIONALLICENCE 700 1- Tsvetkov D. Department of Chemistry, Moscow State University, 119899, Moscow, Russia aut NATIONALLICENCE 773 0- Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 65-71 0023-1584 46:1<65 2005 46 10975 NATIONALLICENCE 856 40 https://doi.org/10.1007/s10975-005-0045-4 text/html Onlinezugriff via DOI Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE NATIONALLICENCE NL-springer