caa a22 4500 475761626 CHVBK 20180406123553.0 cr unu---uuuuu 170329e20000501xx s 000 0 eng 10.1007/BF02494699 doi (NATIONALLICENCE)springer-10.1007/BF02494699 Mechanism of methane activation by electrophiles generated in the AlBr5 system: An MNDO/PM3 study of the potential energy surface of the [AlBr5+CH4] system [Elektronische Daten] [A. Chistyakov, I. Stankevich, N. Gambaryan, I. Akhrem] Fragments of the potential energy surfaces (PES) of the AlBr5 (I) and [AlBr5+CH4] (II) systems were studied by the MNDO/PM3 method. Five local minima corresponding to Br2·AlBr3 donor-acceptor complexes were found on the PES of system I. Two of these complexes have a pronounced ionic character. In system II, among the products of barrierless addition of Br2·AlBr3 complexes to CH4, the methane molecule is activated only in two complexes. These are products of the attack of the most electrophilic AlBr5 complexes on a H atom of the methane molecule. The potential barriers to conversion of these products into complexes with structures formally corresponding to the products of the attack of electrophiles on a C−H bond (the Olah scheme) or the C atom of methane molecule (the Schreiner scheme) were calculated. Kluwer Academic/Plenum Publishers, 2000 methane, bromine, aluminum bromide, complexes Br2·AlBr3, superelectrophiles nationallicence mechanism of electrophilic activation of alkanes nationallicence quantum-chemical calculations, MNDO/PM3 method, potential energy surface nationallicence Chistyakov A. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut Stankevich I. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut Gambaryan N. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut Akhrem I. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/5(2000-05-01), 799-805 1066-5285 49:5<799 2000 49 11172 https://doi.org/10.1007/BF02494699 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02494699 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Chistyakov A. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Stankevich I. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Gambaryan N. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Akhrem I. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/5(2000-05-01), 799-805 1066-5285 49:5<799 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer