Exhaustive Cyanation of the Dodecaborate Dianion: Synthesis, Characterization, and X-ray Crystal Structure of [B₁₂(CN)₁₂]^2–

Abstract

The percyanated dodecaborate anion [B12(CN)12]2– was prepared by reacting [B12I12]2– with CuCN in the presence of a palladium catalyst at elevated pressure and temperature in a microwave reactor. The fully cyanated cluster was isolated as a tetraethylammonium salt in yields of up to 39% and characterized by NMR and IR spectroscopy and mass spectrometry. The crystal structure of a copper complex of the percyanated anion, (CH3CN)3Cu­[μ-B12(CN)12]­Cu­(NCCH3)3, was determined by single-crystal X-ray diffraction.

Properties of gaseouscloso-[B6X6]2−dianions (X = Cl, Br, I)

“…As a weakly coordinating anion, [B 12 Cl 12 ] 2À has been used to stabilize highly reactive cations. [1][2][3][4] [B 12 (CN) 12 ] 2À is the most electronically stable multiply charged anion (MCA) synthesized so far [5][6][7][8] and [B 12 I 12 ] 2À belongs to the most chaotropic anions known. 9 Understanding interactions of the weakly coordinating [B 12 X 12 ] 2À anions with different counterions, 1,2,[10][11][12] solvent molecules, 13 coordinating neutral species, 14 host molecules in supramolecular complexes, [15][16][17] and biomolecules 18,19 is of interest, for example, to boron neutron capture therapy, 20,21 stabilization of reactive cations in synthesis and catalysis, 1,4 battery science, 22 and non-linear optics.…”

KNa0.78Eu0.27In3.80B12S12: a novel hexanary thioborate featuring a B12S12 cluster and diverse InSx (x = 4, 5, 6) units

“…[13][14][15] In contrast to the highly reactive borane with a small molecular weight, [B 12 H 12 ] 2− -based salts are the most stable molecules; this anion survives extended heating in strongly acidic or alkaline solutions. 16,17 Attracted by the specialty of B 12 , many efforts have been made to enrich this special entity. 18 Completely saturated with hydrogen, halogens, or even hydroxyl groups, the boron icosahedra can be obtained in solution.…”

“…13–15 In contrast to the highly reactive borane with a small molecular weight, [B 12 H 12 ] 2− -based salts are the most stable molecules; this anion survives extended heating in strongly acidic or alkaline solutions. 16,17…”

First steps towards a stable neon compound: observation and bonding analysis of [B12(CN)11Ne]−

“…(2 18 The advanced synthesis procedure of the percyano-closo-dodecaborate anion reported here is based on a photochemical reaction, which exchanges iodine substituents in [B 12 I 12 ] 2À with CN groups. This approach was mentioned first by Trofimenko in 1965, but yielded only products with a maximum of 8-9 CN groups.…”

“…At 40 K ion trap Fig. 2 18 and quantum chemically predicted values using the B3LYP/def2-QZVPP method (1.150 and 1.538 Å).…”