1-Me2NH-2-CH2Cl-closo-l-CB11H10. An unusual product from the insertion reaction of Me2NBCl2 with Li2 [7-Me3N-nido-7-CB10H10]

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

“…Their hydrolysis resulted in the free amines [1-R-2-H 2 N-closo-CB 11 H 10 ] À (R = H, Ph, H 2 N, CyHN) as depicted in Scheme 4. Similar insertion reactions of boron have been described previously, [16][17][18] but the groups attached to the boron atom in the 2-position of the resulting carba-closo-dodecaborate anions (e. g. F, Ph, Me 2 N, OA C H T U N G T R E N N U N G (CH 2 ) 4 Cl) are not useful for further derivatizations. Recently, we reported on investigations of the [1-H 2 N-2-F-closo-CB 11 H 10 ] À ion, which was obtained from 7-H 3 N-7-nido-CB 10 H 12 and BF 3 ·OEt 2 , in an analogous reaction to those presented in Scheme 4, [42] and comparable reactions of zwitterionic carboranes 7-RH 2 N-7-nido-CB 10 H 12 are standard procedures for the preparation of amino-substituted 12-vertex closo-metallacarboranes.…”

“…[17] This approach failed for the preparation of 1,2-diaminocarba-closo-dodecaborates, because the attempted insertion of Me 2 NBCl 2 into [7-Me 2 N-7-nido-CB 10 H 10 ] 3À resulted in 1-Me 2 HN-2-CH 2 Cl-closo-CB 11 H 11 . [18] Furthermore, the inner salt 7-H 3 N-closo-CB 11 H 11 was prepared by treatment of Na[closo-CB 11 H 12 ] with H 2 NSO 3 H; subsequent methylation yielded 7-Me 3 N-closo-CB 11 H 11 . [19] Thermal decomposition of [BH 2 A C H T U N G T R E N N U N G (NMe 3 ) 2 ][7-nido-CB 10 H 13 ] resulted in a mixture of the three isomers 2-, 7-, and 12-Me 3 N-closo-CB 11 H 11 , which were separated by chromatography.…”

Carboranes as Lewis Acids: Tetrel Bonding in CB11H11 Carbonium Ylide

“…No V(C,X) disynaptic basins are found for CO 2 and FH, an indication of the poor electron-donating ability of these Lewis bases (LB) with indeed long d(C-X) distances and positive free energies of formation ∆G > 0, hence confirming the unlikely formation of these two complexes. According to the Cambridge structural database(CSD) [32], several tetrel complexes derived from (1) have been characterised [33][34][35][36][37][38][39] where the C(ylide) centre interacts with a nitrogen atom from neutral aminoderivatives including pyridine. These structures are shown in the SI file as Table S13.…”