A two-coordinate boron cation featuring C-B+-C bonding.
Two-coordinate boron cations (R2B(+)), referred to as borinium ions, are chemical species in which the boron bears only four valence electrons, and that are isoelectronic with hypothetical carbon dications (R2C(2+)). Although lone-pair-donating substituents such as amino groups have enabled the isolation of several borinium ions, diarylated and dialkylated borinium derivatives remain entirely unexplored. Here, we present the synthesis, structure and reactivity of the dimesitylborinium ion, which displays unexpectedly high thermal stability. X-ray crystallography and (11)B NMR spectroscopy, supported by density functional theory calculations, reveal that the borinium ion adopts a linear two-coordinate structure in both the solid state and in solution. The boron centre is stabilized by pπ bonding from the mesityl groups and is free from coordination by the counterion or solvent molecules. This diarylborinium ion possesses exceptional Lewis acidity, accepting a pair of electrons from CO2 to cause an unusual deoxygenation reaction.
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Yoshiaki
Y
Shoji
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Naoki
N
Tanaka
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Koichiro
K
Mikami
1] Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan [2] Advanced Elements Chemistry Research Team, RIKEN Centre for Sustainable Resource Science (CSRS) and Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Masanobu
M
Uchiyama
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Takanori
T
Fukushima
D001896:Boron Compounds / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry; D002412:Cations / Q000737:chemistry*; D018360:Crystallography, X-Ray; D058116:Lewis Acids / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction
D001896:Boron Compounds; D002412:Cations; D058116:Lewis Acids; D002245:Carbon Dioxide