title: Synthesis, reactivity and structural studies of selenide bridged carboranyl compounds.
abstract: Reaction of the lithium salt Li[1-R-1,2-closo-C(2)B(10)H(10)] with selenium under mild conditions, followed by hydrolysis gave the diselenide compound (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) in contrast to the well-reported mercapto compounds 1-SH-2-R-1,2-closo-C(2)B(10)H(10) obtained using a similar synthetic procedure. Details for the preparation and X-ray structural characterisation of the new compounds (2-Me-1,2-closo-C(2)B(10)H(10))(2)Se, (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) (R = Me, Ph, ) are specified. To further explore the mechanism of the dimerization reaction, the complex [Au(1-Se-2-Me-1,2-closo-C(2)B(10)H(10))(PPh(3))] was synthesized, confirming the existence of the intermediate Li[1-Se-2-R-1,2-closo-C(2)B(10)H(10)] at the early stages of the reaction before selenium oxidation. Theoretical calculations and cyclic voltammetry (CV) studies were carried out to compare the bonding nature of the sulfur and the selenium analog compounds. It was determined that diselenides have a higher tendency to reduce with respect to the disulfides and all chalcogen atoms were found to be positively charged.
authors.affiliation: Institut de Ciència de Materials de Barcelona, Campus U.A.B., 08193 Bellaterra, Spain.
authors.forename: Anna
authors.initials: A
authors.lastname: Laromaine
authors.forename: Francesc
authors.initials: F
authors.lastname: Teixidor
authors.forename: Raikko
authors.initials: R
authors.lastname: Kivekäs
authors.forename: Reijo
authors.initials: R
authors.lastname: Sillanpää
authors.forename: Massimiliano
authors.initials: M
authors.lastname: Arca
authors.forename: Vito
authors.initials: V
authors.lastname: Lippolis
authors.forename: Eulàlia
authors.initials: E
authors.lastname: Crespo
authors.forename: Clara
authors.initials: C
authors.lastname: Viñas