N‐Heterocyclic Silylenes in Boron Chemistry: Facile Formation of Silylboranes and Silaborinines. Issue 46 (6th October 2016)

• Record Type: Journal Article
• Authors: Gackstatter, Annika; Braunschweig, Holger; Kupfer, Thomas; Voigt, Christian; Arnold, Nicole
• Is Part Of: Chemistry. Volume 22:Issue 46(2016)
• Page Start: 16415
• Page End: 16419
• Publication Date: 2016-10-06
• Subjects: boranes -- density functional theory -- insertion -- ring expansion -- silylenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201603945
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Reaction of a N‐heterocyclic silylene (NHSi) with PhBX2 (X=Cl, Br) readily afforded six‐membered silaborinines through an insertion/ring expansion sequence. Increasing the sterics of the borane from phenyl to duryl enabled the selective generation and isolation of the highly colored silylborane intermediates. Theoretical studies on the mechanism and energetics of the silaborinine formation were fully consistent with the experimental observations. Abstract : Size matters : Reaction of an N‐heterocyclic silylene with aryl‐substituted dihaloboranes ArBX2 (Ar=Ph, Dur; X=Cl, Br) readily afforded either silaborinines (Ar=Ph; insertion/ring expansion) or silylborane intermediates (Ar=Dur; insertion; Dur=2, 3, 5, 6‐tetramethylphenyl).