Strongσ‐Hole Activation on Icosahedral Carborane Derivatives for a Directional Halide Recognition

Abstract

Crystal engineering based on s-hole interactions is an emerging approach for realization of new materials with higher complexity.Neutral inorganic clusters derived from 1,2dicarba-closo-dodecaborane, substituted with-SeMe,-TeMe, and-I moieties on both skeletal carbon vertices are experimentally demonstrated herein as outstanding chalcogen-and halogen-bond donors.I np articular,t hese new molecules strongly interact with halide anions in the solid-state.T he halide ions are coordinated by one or two donor groups (m 1and m 2-coordinations), to stabilizeadiscrete monomer or dimer motifs to 1D supramolecular zigzag chains.C rucially, the observed chalcogen bond and halogen bond interactions feature remarkably short distances and high directionality. Electrostatic potential calculations further demonstrate the efficiency of the carborane derivatives,with V s,max being similar or even superior to that of reference organic halogen-bond donors,s uch as iodopentafluorobenzene.

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane†

“…The result proved the directing ability of methyldithiocarboxyl group toward palladium‐induced selective B—H activation of p ‐carborane, which has been a challenge because of the equivalence of ten B—H bonds. [ 3,18 ]…”

“…[ 1 ] Because of its low‐toxicity, convenient modification as well as thermal and chemical stability, carboranes have played an increasingly important role in fundamental inorganic and organometallic chemistry. [ 2 ] Recently, the rapid development of carborane chemistry allows the design and synthesis of various carborane compounds as a kind of useful tools for supporting and stabilizing new‐type organometallic structures, for instance, carboranyl‐ligand‐supported supramolecular structure, [ 3 ] metallaoradicals, [ 4 ] borylenes, [ 5 ] coinage metal clusters, [ 6 ] tetrylones, [ 7 ] carborane‐containing luminophores. [ 8 ] It is worth noting that the possibility of assembling metallacycles by carboranyl ligand has revealed by the synthesis of p ‐carboranyl dithiamide supported metallacycles.…”

“…[ 8 ] It is worth noting that the possibility of assembling metallacycles by carboranyl ligand has revealed by the synthesis of p ‐carboranyl dithiamide supported metallacycles. [ 3 ] Because of the unique electronic structure and properties of carborane nuclei, such metallacycle structure could have special properties which are hardly found on analogues supported by common organic ligands and hence receive sustained attention.…”