Theoretical study on the photochemistry of furoylazides: Curtius rearrangement and subsequent reactions

Abstract

Organic azides are efficient source of nitrenes, which serve as vigorous intermediates in many useful organic reactions. In this work, the complete active space self-consistent field (CASSCF) and its second-order...

Curtius-Type Rearrangement of Sulfinyl Azides: A Matrix Isolation and Computational Study

“…Among the photolysis products of the azide, two conformers (syn/anti) of the Curtius rearrangement product CF 3 NSO at 1308.5/1291.1 and 1199.7/1169.1 cm −1 can be clearly identified by comparison with its gas-phase spectrum 65,66 at 1310 and 1210 cm −1 for the ν asym (OSN) and ν asym (CF 3 ) modes, respectively. The observed 15 N-isotopic shifts (Δν) of 17.4 and 14.6 cm −1 for the ν asym (OSN) mode when using 15 Nenriched azide as the precursor further support the identification (Figure S13). Formation of the isomeric CF 3 SNO is also evident from the very broad IR band at 1657.5 cm −1 for the ν(NO) mode, and it is close to the frequency of 1660 cm −1 in its gas-phase IR spectrum.…”

Validating experiments for the reaction H2 + NH2− by dynamical calculations on an accurate full-dimensional potential energy surface

“…As has been detailed in our previous work, [36][37][38][39][40][41][42][43][44][45] developing PESs consists of three procedures: sampling configurations in dynamical relevant regions, calculating their energies, and fitting them. For ion-molecule reactions, the long-range interaction plays a key role in their dynamics and kinetics.…”

“…30 For either quasi-classical trajectory (QCT) or quantum dynamical (QD) calculations, a reliable fulldimensional potential energy surface (PES) is required. 31 Thanks to advances in various neural network (NN)-based fitting methods, [32][33][34][35] reliable full-dimensional PESs for reactive systems with up to seven atoms [36][37][38][39][40][41][42][43][44][45][46][47][48] are reported by fitting hundreds of thousands of configurations, whose energies were determined at the explicitly correlated CCSD(T) with the AVTZ basis set (CCSD(T)-F12a/AVTZ). 49,50 However, due to the longrange interactions between the negatively charged ions and the neutral molecules, 2 the PES of (R1) covers a huge configuration space, particularly in the reactant or product channels, making the construction of the full-dimensional accurate PES more challenging.…”

Nitrene formation is the first step of the thermal and photochemical decomposition reactions of organic azides

“…For example, they are important components in click chemistry [1][2][3] or synthesis of energetic materials. [4][5][6][7][8][9][10][11][12] Most of these applications as well as their exceptional reactivity arise from their ability to generate nitrene intermediates after N 2 extrusion. [13][14][15][16][17] Although organic azides are known for more than a century, 18 the decomposition reaction mechanism at an atomistic level is still under discussion.…”