Abstract
The electronic structure of carbenes arises from the occupation of a σ and a π frontier orbital. While parent methylene possesses a triplet ground state (σ1π1), substituents are capable of stabilizing the singlet (σ2π0 or σ0π2) by altering the frontier orbital energies. Here, we reveal that the 1,2[I]-shift isomer of 2-iodopyridine, the N-iodo Hammick intermediate, features a resonance between its carbene σ and N–I bond σ* orbitals, rendering them frontier orbitals. This singlet carbene is efficiently generated via UV photolysis of 2-iodopyridine in solid neon at 4.4 K and reacts with molecular hydrogen − but not deuterium − via N–I bond cleavage enabled by quantum tunnelling. Our findings introduce an unprecedented carbene class, unlocking new opportunities for reactivity and electronic structure explorations.
Supplementary materials
Title
Supplementary Materials for Hydrogen activation by a σσ*-carbene through quantum tunnelling
Description
additional IR and UV/vis spectra, computational data, IR spectroscopy data, cartesian coordinates and energies, instanton theory computations
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