Theoretical investigation of the isomerization pathways of diazenes: torsion vs. inversion

Abstract

Ab initio classical trajectory simulations show that diazenes isomerize via out-of-plane torsion and not in-plane inversion due to a centrifugal barrier.

Activation of ammonia and hydrazine by electron rich Fe(ii) complexes supported by a dianionic pentadentate ligand platform through a common terminal Fe(iii) amido intermediate

“…It is likely that the trans-diazene is strongly favored for steric reasons, and we did not explore the path to formation of the cis-isomer. While some structurally characterized cis-diazene complexes exist, 79,80 they are favored by constraints imposed by the ligand systems employed and most adopt trans structures for both steric 51,70-72 and electronic 81,82 reasons.…”

“…they are favored by constraints Please do not adjust margins Please do not adjust margins imposed by the ligand systems employed and most adopt trans structures for both steric51,[70][71][72] and electronic81,82 reasons.…”

Trajectory Surface Hopping Nonadiabatic Molecular Dynamics with Kohn–Sham ΔSCF for Condensed-Phase Systems

“…NRD pathways of the electronically excited 1 ππ * state of ethylene were thoroughly investigated in a number of previous studies. ,− The second system we studied is the diimide molecule, the simplest diazo compound. It is isoelectronic to ethylene, and like ethylene it has been used in a number of theoretical studies since its discovery. − While the isomerization reaction between its trans and cis conformers in the ground electronic state has been of great interest, ,,− only a small number of studies have examined diimide’s dynamics in the excited states. Tavernelli and coauthors have simulated a few trajectories in the gas phase for both conformers initiated in the first singlet excited state and examined the influence of initial conditions and the use of a thermostat in their NA-MD simulations on the diimide NRD mechanism .…”

Activation of Ammonia and Hydrazine by Electron Rich Fe(II) Complexes Supported by a Dianionic Pentadentate Ligand Platform Through a Common Terminal Fe(III) Amido Intermediate

“…It is likely that the trans-diazene is strongly favored for steric reasons, and we did not explore the path to formation of the cis-isomer. While some structurally characterized cis-diazene complexes exist, [76][77] they are favored by constraints imposed by the ligand systems employed and most adopt trans structures for both steric 49,[67][68][69] and electronic [78][79] reasons.…”