Nitrene formation is the first step of the thermal and photochemical decomposition reactions of organic azides
Fecha
2022Versión
Acceso abierto / Sarbide irekia
Tipo
Artículo / Artikulua
Versión
Versión publicada / Argitaratu den bertsioa
Impacto
|
10.1039/D1CP05785E
Resumen
In this work, the decomposition of a prototypical azide, isopropyl azide, both in the ground and excited states, has been investigated through the use of multiconfigurational CASSCF and MS-CASPT2 electronic structure approaches. Particular emphasis has been placed on the thermal reaction starting at the S0 ground state surface. It has been found that the azide thermally decomposes via a stepwise ...
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In this work, the decomposition of a prototypical azide, isopropyl azide, both in the ground and excited states, has been investigated through the use of multiconfigurational CASSCF and MS-CASPT2 electronic structure approaches. Particular emphasis has been placed on the thermal reaction starting at the S0 ground state surface. It has been found that the azide thermally decomposes via a stepwise mechanism, whose rate-determining step is the formation of isopropyl nitrene, which is, in turn, the first step of the global mechanism. After that, the nitrene isomerizes to the corresponding imine derivative. Two routes are possible for such a decomposition: (i) a spin-allowed path involving a transition state; and (ii) a spinforbidden one via a S0/T0 intersystem crossing. Both intermediates have been determined and characterised. Their associated relative energies have been found to be quite similar, 45.75 and 45.52 kcal mol1, respectively. To complete this study, the kinetics of the singlet and triplet channels are modeled with the MESMER (Master Equation Solver for Multi-Energy Well Reactions) code by applying the RRKM and Landau Zener (with WKB tunnelling correction) theories, respectively. It is found that the canonical rate-coefficients of the singlet path are 2-orders of magnitude higher than the ratecoefficients of the forbidden reaction. In addition, the concerted mechanism has been investigated that would lead to the formation of the imine derivative and nitrogen extrusion in the first step of the decomposition. After a careful analysis of CASSCF calculations with different active spaces and their comparison with single electronic configuration methods (MP2 and B3LYP), the concerted mechanism is discarded. [--]
Materias
Organiz azides,
Isopropyl nitrene,
CASSCF,
MS-CASPT2
Editor
Royal Society of Chemistry
Publicado en
Physical Chemistry Chemical Physics, 2022, 24 ,pp. 5109-5115
Departamento
Universidad Pública de Navarra. Departamento de Ciencias /
Nafarroako Unibertsitate Publikoa. Zientziak Saila /
Universidad Pública de Navarra/Nafarroako Unibertsitate Publikoa. Institute for Advanced Materials and Mathematics - INAMAT2
Versión del editor
Entidades Financiadoras
This work has been supported by projects UMA18-FEDER-JA-049 and P18-RT-4592 of Junta de Andalucía and FEDER founds.