Preparation and chemistry of the B9H12Se- and B9H12Te- ions

closo‐TeB5Cl5 und closo‐TeB11Cl11 – polyedrische Telluraborane mit ungewöhnlich langen Raumdiagonalen: Synthese und Bindungsstudien an innovativen oktaedrischen und ikosaedrischen Geometrien

“…Die allgegenwärtige Bildung von closo‐ Clustern spiegelt die Tendenz wider, das thermodynamisch günstigste Produktgemisch zu erhalten. Erste Studien zur Insertion der Chalkogene Schwefel und Selen veranlassten uns, diese Chemie auf die Synthese von halogenierten Telluraboranen zu erweitern, da neben einigen lose verwandten Metall‐Clusterkomplexen [6a,d,e] bisher nur drei neutrale perhydrierte Beispiele (d. h. nido ‐TeB 9 H 11 , [6c] nido ‐TeB 10 H 12 [6a] und closo ‐TeB 11 H 11 [6b] ) bekannt sind. Hier berichten wir über die Synthese des ersten oktaedrischen Telluraboran‐Motivs, closo ‐TeB 5 Cl 5 ( 1 ) und des neuen ikosaedrischen Telluraborans closo ‐TeB 11 Cl 11 ( 2 ).…”

The Telluraboranes closo‐TeB5Cl5 and closo‐TeB11Cl11 with Exceptionally Long Body Diagonals: Synthetic and Bonding Motifs for Innovative Octahedral and Icosahedral Geometries

“…The ubiquitous formation of closo ‐clusters reflects the tendency to yield the most thermodynamically favorable product mixture. The first results of the insertion of the chalcogens sulfur and selenium prompted our attempts to extend this chemistry to the synthesis of halogenated telluraboranes, because only three neutral hydrogenated [6a–d] examples (i.e. nido ‐TeB 9 H 11 , [6c] nido ‐TeB 10 H 12 [6a] and closo ‐TeB 11 H 11 [6b] ) have been reported in addition to some related metal complexes [6a,d,e] .…”

“…The first results of the insertion of the chalcogens sulfur and selenium prompted our attempts to extend this chemistry to the synthesis of halogenated telluraboranes, because only three neutral hydrogenated [6a–d] examples (i.e. nido ‐TeB 9 H 11 , [6c] nido ‐TeB 10 H 12 [6a] and closo ‐TeB 11 H 11 [6b] ) have been reported in addition to some related metal complexes [6a,d,e] . Here we report the synthesis of two new telluraboranes including the first octahedral closo ‐TeB 5 Cl 5 and the icosahedral closo ‐TeB 11 Cl 11 motifs.…”

Chlorinated polyhedral selenaboranes revisited by joint experimental/computational efforts: the formation of closo-1-SeB9Cl9 and the crystal structure of closo-SeB11Cl11

“…4–6 However, the area of chalcogenaboranes turned out to be under-researched and just a few polyhedral selenaboranes Se x B y H z are known. 7 Recently, we have reported on the synthesis and DFT/GIAO/NMR study of the perhalogenated selenaboranes closo -SeB 5 Cl 5 ( 1a ) and closo -SeB 11 Cl 11 ( 1b ) by the co-pyrolysis reaction of a 9 : 1 mixture of B 2 Cl 4 with Se 2 Cl 2 in vacuo at 330 °C. 8 It is well known from the thermal disproportionation reactions of B 2 Cl 4 with n -vertex boron subchlorides B n Cl n ( n = 8–12) 9 that the size n and the distribution of products strongly depend on the reaction temperature and time under thermolytic conditions: higher pyrolysis temperatures augment the amount of active BCl species (see eqn (1)) and thus increase the probability of the formation of larger cages.…”