Year: 2025
Type: article
Abstract: We report the characterization of bromopyridin‐2‐ylidene, the N‐bromo‐Hammick intermediate, isolated in solid neon at 4.4 K. Computations (B2PLYP, NEVPT2), IR, and UV/vis spectroscopy characterize this intermediate as a singlet carbene with a vacant σ*‐type frontier orbital. This unusual electronic structure (σ 2 σ* 0 ) allows the carbene to isomerize to its more stable pyridine tautomer via a planar transition state, avoiding the deviation from planarity seen in other singlet carbenes. The compound's reaction with molecular hydrogen faces a minor but prohibitive barrier (8.4 kcal mol −1 ) at the low temperatures of the experiment.
Source: Chemistry - A European Journal
Authors: Virinder Bhagat, J. Philipp Wagner
Institutions: University of Tübingen, University of Bremen
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,640
OpenAlex ID: W4414559895