title: A DFT investigation of alkyne bromination reactions.
abstract: [Structure: see text]. A DFT calculation study of the addition reaction between molecular bromine and the number of symmetrical or unsymmetrical substituted alkynes 1 (R-CC-R'), where R = R' = H (1a), Me (1b), t-Bu (1c), or Ph (1d), or R = H and R' = Me (1e), t-Bu (1f), or Ph (1g), was performed. Two possible reactions were checked: (a) the reactions suitable for the gas-phase interactions, which start from a 1:1 Br2-alkyne pi-complex and do not enter into a 2:1 Br2-alkyne pi-complex; and (b) the processes passing through a 2:1 Br2-alkyne pi-complex, which look more realistic for the reactions in solutions. The structures of the starting reactants and the final products as well as the possible stable intermediates have been optimized. The transition states of the predicted process have been found. Both trans- and cis-dibromoalkenes (2 and 3) may ensue without the formation of ionic intermediates from a pi-complex of two bromine molecules with the alkyne (solution reactions). The geometry around the double bond forming in dibromoalkenes strongly depends on the nature of the substituents at the triple bond. The "cluster model" was also used for the prediction of solvent influence on the value of the activation barrier of the but-2-yne (1b) bromination reaction.
authors.affiliation: Chemistry Department, Moscow State University, B-234 Leninskie Gory, 119899 Moscow, Russia.
authors.forename: Maxim V
authors.initials: MV
authors.lastname: Zabalov
authors.forename: Sergey S
authors.initials: SS
authors.lastname: Karlov
authors.forename: Dmitri A
authors.initials: DA
authors.lastname: Lemenovskii
authors.forename: Galina S
authors.initials: GS
authors.lastname: Zaitseva