Reactions of Frustrated Lewis Pairs with Chloro‐Diazirines: Cleavage of N=N Double Bonds

• Published in: Angewandte Chemie International Edition Vol. 61; no. 37; pp. e202209241 - n/a
• Main Authors: Mandal, Dipendu, Chen, Ting, Qu, Zheng‐Wang, Grimme, Stefan, Stephan, Douglas W.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 12.09.2022; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Bond Cleavage; Chemistry; Chemistry, Multidisciplinary; Density Functional Theory; Diazirine; Frustrated Lewis Pairs; Mechanistic Study; Nitrogen; Phosphine; Phosphines; Physical Sciences; Science & Technology; Zwitterions; ACTIVATION; ACCURATE; DESIGN; Bond Cleavage; Mechanistic Study; Diazirine; BORANE; Frustrated Lewis Pairs; N-2; Density Functional Theory; CHEMISTRY; NITROGEN; BASIS-SETS; COSMO
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202209241

The reactions of FLPs with diazomethanes leads to the rapid loss of N2. In contrast, in this work, we reported reactions of phosphine/borane FLPs with chlorodiazirines which led to the reduction of the N=N double bond, affording linked phosphinimide/amidoborate zwitterions of the general form R3PNC(Ar)NR′BX(C6F5)2. A detailed DFT mechanistic study showed that these reactions proceed via FLP addition to the N=N bond, followed by subsequent group transfer reactions to nitrogen and capture of the halide anion. While the reactions of FLPs with diazomethanes are known to lead to rapid loss of N2, reactions of phosphine/borane FLPs with chlorodiazirines prompt N=N double bond cleavage, affording linked phosphinimide/amidoborate zwitterions of the general form R3PNC(Ar)NR′BX(C6F5)2. A detailed DFT mechanistic study shows that these reactions proceed via FLP addition to the N=N bond.