title: Thiocyanation of closo-dodecaborate B(12)H(12)(2-). A novel synthetic route and theoretical elucidation of the reaction mechanism.
abstract: Although vast experimental experience has been accumulated about the reactions of icosahedral B(12)H(12)(2-) borane cages, little is known about the mechanisms by which these reactions proceed. To address this issue, we have chosen the thiocyanation of B(12)H(12)(2-) and have studied this reaction using both experimental and theoretical methods. First, we present a novel and more convenient synthetic route using in situ generated thiocyanogen, (SCN)(2). The synthesized disubstituted product B(12)H(10)(SCN)(2)(2-) is exclusively the meta positional isomer, as confirmed by the X-ray crystallographic analysis. The quantum chemical calculations at the B3LYP/def2-TZVP//RI-PBE/def2-SVP level show that the free energy differences between the ortho, meta, and para disubstituted species are very small and as such cannot explain the observed positional preferences. The calculations of the kinetic aspects reveal that the reaction is best described as an electrophilic substitution. The calculated isomer preferences for the second SCN substituent are meta > para > ortho. The major outcome of this work is a clear and consistent picture of the electrophilic substitution reaction mechanism of the thiocyanation of B(12)H(12)(2-), thus contributing to our understanding of the general features of boron hydride reactivity.
authors.affiliation: Institute of Organic Chemistry and Biochemistry of the Academy of Sciences of the Czech Republic, Gilead Sciences Research Center, Flemingovo Namesti 2, 166 10 Prague 6, Czech Republic.
authors.forename: Martin
authors.initials: M
authors.lastname: Lepsík
authors.forename: Martin
authors.initials: M
authors.lastname: Srnec
authors.forename: Jaromír
authors.initials: J
authors.lastname: Plesek
authors.forename: Milos
authors.initials: M
authors.lastname: Budesínský
authors.forename: Blanka
authors.initials: B
authors.lastname: Klepetárová
authors.forename: Drahomír
authors.initials: D
authors.lastname: Hnyk
authors.forename: Bohumír
authors.initials: B
authors.lastname: Grüner
authors.forename: Lubomír
authors.initials: L
authors.lastname: Rulísek