Synthesis of Highly Iodinated Icosahedral Mono- and Dicarbon Carboranes

A Camouflagednido-Carborane Anion: Facile Synthesis of Octa-B-methyl-1,2-dicarba-closo-dodecaborane(12) and Its Deboration Reaction

“…Para-carborane (3) yielded the per-B-iodinated compound, whereas 1 and 2 gave exclusively the 4,5,7,8,9,10,11,12-and 4,5,6,8,9,10,11,12-octaiodo derivatives, respectively. [16] The exhaustive ethylation of of 1 and 2 was attempted by using EtBr, or EtI and AlCl 3 . As previously described, [17] up to four ethyl groups can be readily introduced; however, polymeric material formed upon continued heating.…”

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)

“…[10] In a related reaction the [1-Me 2 N-closo-CB 11 H 11 ] À ion was obtained. [10] A number of derivatives of these anions have been prepared by using salts of 2 or [1-Me 2 N-closo-CB 11 H 11 ] À as starting materials, [1] for example [1-Ph(O)C=MeN-closo-CB 11 H 11 ] À , [11] 1-R 3 N-12-Icloso-CB 11 H 10 (R = Me, 4-pentylquinuclidin-1-yl), [12,13] and [1-H 2 N-closo-CB 11 Hal 11 ] À (Hal = I, Cl). [12,14] In addition, polymers with the 1-aminocarba-closo-dodecaborane fragment have been obtained.…”

“…[10] A number of derivatives of these anions have been prepared by using salts of 2 or [1-Me 2 N-closo-CB 11 H 11 ] À as starting materials, [1] for example [1-Ph(O)C=MeN-closo-CB 11 H 11 ] À , [11] 1-R 3 N-12-Icloso-CB 11 H 10 (R = Me, 4-pentylquinuclidin-1-yl), [12,13] and [1-H 2 N-closo-CB 11 Hal 11 ] À (Hal = I, Cl). [12,14] In addition, polymers with the 1-aminocarba-closo-dodecaborane fragment have been obtained. [15] Synthesis of [1-H 2 N-2-R-closo-CB 11 H 11 ] À was achieved by boron insertion; for example by Abstract: The first primary 2-aminocarba-closo-dodecaborates [1-R-2-H 2 Ncloso-CB 11 H 10 ] À (R = H (1), Ph (2)) have been synthesized by insertion reactions of (Me 3 Si) 2 NBCl 2 into the trianions [7-R-7-nido-CB 10 The thermal properties were investigated by differential scanning calorimetry (DSC).…”

“…[21] Its derivatives have emerged as widely used starting materials for the preparation of boron-rich compounds. [6,8,22] They have been applied for the preparation of ionic liquids with [R 3 N-closo-B 12 H 11 ] À ions (R = alkyl), [23] as building blocks in ionomers, [24] for compounds with nonlinear optical (NLO) properties, [25] as weakly coordinating anions [R 3 N-closo-B 12 F 11 ] À (R = H, alkyl), [26] as ligands in transition-metal chemistry, for example in [RuCOA C H T U N G T R E N N U N G (PPh 3 ) 2 (H 2 N-closo-B 12 H 11 )], [27] and for pharmaceuticals, [6,28] for example, for boron neutron capture therapy (BNCT). [29] Exhaustive treatment of [closo-B 12 H 12 ] 2À with H 2 NSO 3 H resulted in double substitution giving (H 3 N) 2 -closo-B 12 H 10 .…”

Carbon Extrusion/Cluster Contraction: Synthesis of the Fluorinated Cyano‐closo‐Undecaborate K2[3‐NC‐closo‐B11F10]

“…[18] [ (n = 1, 2) was confirmed by NMR spectroscopy and by mass spectrometry (Figure 1). First attempts to convert other aminocarborate anions, such as [1-H 2 N-closo-CB 11 H 11 ] À , [21] [1-H 2 N-closo-CB 11 I 11 ] À , [22] and [1-H 2 N-2-F-closo-CB 11 H 10 ] À , [23] into the corresponding cyano-closo-undecaborate anions failed. Hence, the carbon extrusion/cluster contraction reaction presented herein might be a unique property of highly fluorinated boron clusters.…”