Cleavage of the N≡N Triple Bond and Unpredicted Formation of the Cyclic 1,3‐Diaza‐2,4‐Diborete (FB)₂N₂ from N₂ and Fluoroborylene BF

Abstract

Ac omplete cleavage of the triple bond of N 2 by fluoroborylene (:BF) was achieved in al ow-temperature N 2 matrix by the formation of the four-membered heterocycle FB(m-N) 2 BF,w hich lacks at rans-annular N À Nb ond. Additionally,t he linear complex FB = N À N = BF and cyclic FB(h 2 -N 2 )w ere formed. These novel species were characterized by their matrix infrared spectra and quantum-chemical calculations.The puckered four-membered-ring B 2 N 2 complex shows ad elocalized aromatic two-electron p-system in conjugation with the exo-cyclic fluorine p lone pairs.T his work may contribute to ar ational design of catalysts based on borylene for artificial dinitrogen activation.Scheme 1. Five different binding modes of N 2 to borylenes.

Photoinduced Dual C−F Bond Activation of Hexafluorobenzene Mediated by Boron Atom

“…Apparently, the first three bands (1648.3, 1524.0 and 1495.4 cm −1 ) with quite small 11 B shifts (0.4, 1.1 and 1.5 cm −1 ) belong to the C−C stretching vibrations. The 1389.3 cm −1 band, showing a very large boron isotopic shift (33.7 cm −1 ) is the characteristic stretching vibration of the BF moiety in C 6 F 5 BF, which is red‐shifted comparing to those of 10 BF (1412.2 cm −1 , N 2 ‐matrix) [24] and FBTiF 2 (1404 cm −1 , Ar‐matrix) [25] . The bands at 939.4 and 623.3 cm −1 show large isotopic shifts (9.5 and 9.2 cm −1 ), indicating that these absorptions can be mainly assigned to the B−C deformation modes.…”

Predicting dinitrogen activation by borenium and borinium cations

“…16 Very recently, Riedel, Wang and co-workers achieved the cleavage of the triple bond in N 2 by fluoroborylene (:BF) in a low- temperature N 2 matrix via the formation of two novel cyclic fluorodiazaborirines and a linear isomer. 17 Also, Eunsung Lee and co-workers reported that the anionic aminocarbene radical can decrease the activation barrier of aminocarbene in a reaction with N 2 . 18 Frustrated Lewis pair (FLP) chemistry has been widely utilized in the activation of a growing range of small molecules, such as H 2 , CO 2 , SO 2 , olefins, CO and so on.…”