caa a22 4500 463239814 CHVBK 20180405153309.0 cr unu---uuuuu 170326e20070101xx s 000 0 eng 10.1007/s10947-007-0154-1 doi (NATIONALLICENCE)springer-10.1007/s10947-007-0154-1 Yudanov I. G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk aut Mechanism of olefin epoxidation with transition metal peroxo complexes: DFT study [Elektronische Daten] [I. Yudanov] Using density functional calculations over the last decade led to considerable progress in understanding the mechanism of olefin epoxidation with Ti, V, Mo, W, and Re peroxo complexes. According to calculations, the reaction occurs by direct electrophilic transfer of one of the atoms of the peroxo group to the olefin. The alternative stepwise mechanism, which has been discussed for a long time and suggested the formation of a metallocyclic intermediate, is characterized by higher activation barriers than direct transfer. The electrophilic character of the direct transfer of oxygen was interpreted at the level of molecular orbital analysis as interaction between the HOMO of the olefin π(C-C) and the LUMO of the peroxo group σ*(O-O). The factors determining the activity of various metal complexes in epoxidation were examined in relation to the ligand environment and the structure of the peroxo group. Springer Science+Business Media, Inc., 2007 Ti, V, Cr, Mo, W, and Re peroxo complexes nationallicence epoxidation of olefins nationallicence oxygen transfer nationallicence activation barriers nationallicence ab initio calculations nationallicence Journal of Structural Chemistry Springer US 48(2007-01-01), S111-S124 0022-4766 48<S111 2007 48 10947 https://doi.org/10.1007/s10947-007-0154-1 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10947-007-0154-1 text/html Onlinezugriff via DOI NATIONALLICENCE 100 1- Yudanov I. G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk aut NATIONALLICENCE 773 0- Journal of Structural Chemistry Springer US 48(2007-01-01), S111-S124 0022-4766 48<S111 2007 48 10947 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer