caa a22 4500 467947309 CHVBK 20180405193738.0 cr unu---uuuuu 170328e20050101xx s 000 0 eng 10.1007/PL00021978 doi (NATIONALLICENCE)springer-10.1007/PL00021978 (NATIONALLICENCE)springer-10.1007/s10975-005-0027-6 Kinetic parameters of the cyclization and decyclization reactions of nitrogen- and oxygen-containing radicals [Elektronische Daten] [T. Denisova, E. Denisov] The intersecting parabolas model is used to analyze experimental data for the following radical cyclization and decyclization reactions: RCH=CH(CH2)nN·R1 → cyclo-[NR1CH(CH2)n]C·HR,R(CH2)2OOCH2C·HR → cyclo-[RCHOCH2] + RCH2CH2O·, cyclo-[(CH2)nOOCHC· HR] → cyclo-[RCHOCH](CH2)nO·, cyclo-[(CH2)nOC·RO] → RC(O)O(CH2) n−1C·H2, and cyclo-[(CH2)nCHO·] → CH(O)(CH2) n−1C·H2. The activation energy of the thermally neutral reaction (E e,0) is calculated for each class of reactions. E e,0 depends on the electronegativity of the heteroatom Y of the reaction center C $$\underline \cdots$$ C...Y, the force constants of the reacting bonds, and the strain energy of the ring formed. For the cyclization and decyclization of six-membered rings, the empirical relationship between the elongation of the reacting bonds in the transition state (r e) and the difference in electronegativity (ΔEA) between the C and Y atoms (Y = C, N, O) has the form r e ×1011, m = 3.83 − 0.0198(ΔEA, kJ/mol). MAIK "Nauka/Interperiodica”, 2005 Denisova T. Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432, Moscow oblast, Russia aut Denisov E. Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432, Moscow oblast, Russia aut Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 1-9 0023-1584 46:1<1 2005 46 10975 https://doi.org/10.1007/PL00021978 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/PL00021978 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Denisova T. Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432, Moscow oblast, Russia aut NATIONALLICENCE 700 1- Denisov E. Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432, Moscow oblast, Russia aut NATIONALLICENCE 773 0- Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 1-9 0023-1584 46:1<1 2005 46 10975 NATIONALLICENCE 856 40 https://doi.org/10.1007/s10975-005-0027-6 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