title: Chlorination of 1-Carba-closo-dodecaborate and 1-Ammonio-closo-dodecaborate Anions.
abstract: Fully chlorinated carborate and dodecaborate cages such as [CHB11Cl11]-and [Me3NB12Cl11]-are prominent examples of valuable and chemically rather inert weakly coordinating anions. While both anions can be obtained by chlorination of the precursors [CH12B11]-and [H3NB12H11]-with SO2Cl2followed by methylation for the synthesis of [Me3NB12Cl11]-, best results were found using photochemical chlorination with SO2Cl2for [CH12B11]-and thermal chlorination with SO2Cl2for [H3NB12H11]-. The hexachlorinated anion [n-Pr3NB12H5Cl6]-was formed readily within 30 min by chlorination of [n-Pr3NB12H11]-, but attempts to synthesize isopropyl-substituted ammonio-dodecaborates with a higher chlorination number resulted in the formation of mixtures and partial decomposition. The silver and trityl salts of the anions [CHB11Cl11]-, [Me3NB12Cl11]-, and [n-Pr3NB12H5Cl6]-as well as the contact ion-pair [Et2Al][Me3NB12Cl11] were also prepared, and the compounds [Ag(NCMe)][Me3NB12Cl11], [Et2Al][Me3NB12Cl11], and [Et4N][i-Pr3NB12H5Cl6] were also characterized by X-ray crystallography.
authors.affiliation: Department of Chemistry, Florida Institute of Technology , 150 West University Boulevard, Melbourne, Florida 32901, United States.
authors.forename: Mahmoud
authors.initials: M
authors.lastname: Saleh
authors.affiliation: Department of Chemistry and Biochemistry, University of Oklahoma , 101 Stephenson Parkway, Norman, Oklahoma 73019-5251, United States.
authors.forename: Douglas R
authors.initials: DR
authors.lastname: Powell
authors.affiliation: Department of Chemistry, Florida Institute of Technology , 150 West University Boulevard, Melbourne, Florida 32901, United States.
authors.forename: Rudolf J
authors.initials: RJ
authors.lastname: Wehmschulte