caa a22 4500 605488002 CHVBK 20210128100453.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00214-015-1648-0 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1648-0 Revisiting the Kolbe-Schmitt reaction of sodium 2-naphthoxide [Elektronische Daten] [Svetlana Marković, Igor Đurović, Zoran Marković] The mechanism of the carboxylation reaction of sodium 2-naphthoxide (NaphONa) was investigated in the positions 1, 3, and 6 by means of three methods: B3LYP, B3LYP-D2, and M06-2X. While B3LYP failed to describe reaction pathways 3 and 6, B3LYP-D2 (owing to the empirical correction term) and M06-2X (owing to the way it has been parameterised) produced relatively consistent results which create completely new picture of the reaction mechanism. It was found that the reactants can build two NaphONa-CO2 complexes, of which only one can be further transformed to the reaction products. In this new NaphONa-CO2 complex, the CO2 moiety is perfectly positioned to perform electrophilic attacks on all three nucleophilic carbons of the naphthalene ring. Each reaction pathway occurs via two transition states and one intermediate. The mechanism involves a bimolecular reaction step for proton transfer, which requires notably smaller activation barrier than previously considered intramolecular rearrangement. It was shown that reaction pathway 6 is unfavourable from both kinetic and thermodynamic points of view. On the other hand, pathways 1 and 3 are competitive: pathway 1 requires lower activation barriers, but pathway 3 yields the most stable reaction product. These thermochemical results are in good agreement with the experimentally determined products ratio. Springer-Verlag Berlin Heidelberg, 2015 Carboxylation reaction nationallicence Sodium hydroxy naphthoates nationallicence Mechanistic study nationallicence B3LYP-D2 and M06-2X calculations nationallicence Marković Svetlana Faculty of Science, University of Kragujevac, Radoja Domanovića 12, 34000, Kragujevac, Serbia aut Đurović Igor Faculty of Agronomy, University of Kragujevac, Cara Dušana 34, 32000, Čačak, Serbia aut Marković Zoran State University of Novi Pazar, Vuka Karadžića bb, 36300, Novi Pazar, Serbia aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/4(2015-04-01), 1-9 1432-881X 134:4<1 2015 134 214 https://doi.org/10.1007/s00214-015-1648-0 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1648-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Marković Svetlana Faculty of Science, University of Kragujevac, Radoja Domanovića 12, 34000, Kragujevac, Serbia aut NATIONALLICENCE 700 1- Đurović Igor Faculty of Agronomy, University of Kragujevac, Cara Dušana 34, 32000, Čačak, Serbia aut NATIONALLICENCE 700 1- Marković Zoran State University of Novi Pazar, Vuka Karadžića bb, 36300, Novi Pazar, Serbia aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/4(2015-04-01), 1-9 1432-881X 134:4<1 2015 134 214