Nucleophilic Substitution Reactions in the [B 3 H 8 ] - Anion in the Presence of Lewis Acids

• Published in: Molecules (Basel, Switzerland) Switzerland), 2022-01, Vol.27 (3), p.746
• Main Authors: Shulyak, Alexandra T, Bortnikov, Evgeniy O, Selivanov, Nikita A, Grigoriev, Mikhail S, Kubasov, Alexey S, Zhdanov, Andrey P, Bykov, Alexander Y, Zhizhin, Konstantin Y, Kuznetsov, Nikolai T
• Format: Article
• Language: English
• Subjects: Acids; Aluminum chloride; Anions; boranes; borohydrides; boron; Chromatography; cluster; Copper chloride; Hafnium compounds; Halides; Iodine; Magnetic resonance spectroscopy; Manganese; NMR; NMR spectroscopy; Nuclear magnetic resonance; nucleophilic substitution; octahydrotriborate; Substitution reactions; X-ray diffraction; Zirconium
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27030746

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph P, Ph P-(CH ) -PPh (dppe), Ph As, Et N, PhNH , C H N, CH CN, Ph CHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [B H Nu] are obtained. It is found that the use of TiCl , AlCl , ZrCl , HfCl , CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [B H -HMXn ], which was detected by NMR spectroscopy. The structures of [Ph P·B H ] and [PhNH ·B H ] were determined by X-ray diffraction.