Photochemistry of Salicylaldoxime in Solid Argon: An Experimental and Theoretical Study

Abstract

The photochemistry of salicylaldoxime in solid argon has been investigated by FTIR spectroscopy and DFT calculations. The salicylaldoxime molecule trapped in the matrix from the vapor above the solid sample has the most stable syn1 conformation with an intramolecular hydrogen bond. Irradiation (λ Ͼ 320 nm) leads to conversion of the syn1 conformer into the syn3 one, in which the C(H)NOH and (C)OH groups are rotated around the C-C and C-O bonds, respectively, and the intramolecular hydrogen bond is broken. The photochemistry of syn3 involves three possible routes: (i) conversion of syn3 into anti2 conformer, this process requires rearrangement of the NOH group with respect to the

Synthesis, Spectroscopic, Structural and Quantum Chemical Studies of a New Imine Oxime and Its Palladium(II) Complex: Hydrolysis Mechanism

“…It can be seen that the experiment has a better correlation with the calculations. In the IR spectra of nppeieoH, the O–H stretching vibration of the oxime was calculated at 3659 cm −1 , while observed at 3258 cm −1 [54,55,56]. The deviation between the experimental and calculated values seems to be significant for the hydroxyl group frequencies with a difference of 401 cm −1 .…”

Light induced reactions in cryogenic matrices

“…The hydrogen bonded syn1 (S1) conformer was trapped in the matrix from the vapour of the compound; syn3 (S3) corresponds to the primary photoproduct, while anti2 (A2) and the 2-cyanophenol/water complex (C) result from secondary reactions of S3. 35 which would need more energy. Once the chelated form isomerizes, nonchelated forms can decarbonylate, according to the authors probably after np* excitation to the S 3 state.…”

“…35 The salicylaldoxime molecule trapped in the matrix from the vapour above the solid sample has the most stable syn1 conformation, with an intramolecular hydrogen bond. No other salicylaldoxime conformers were detected in the spectra of the matrices recorded directly after deposition, which is in accord with the calculated abundance of syn1 (equal to ca.…”

“…35 The elucidation of the involved mechanism was greatly aided by experiments undertook using partially deuterated [D 2 ]salicylaldoxime. Salicylaldoxime first photodissociates into Ph(OH)HC¼N and OH radicals.…”

Density Functional Study of the Reaction Mechanism of Two Oxiimine Alcohol Formations and Their Novel Rearrangements

“…The reactivity of the oxime group and its metal coordination capability have been studied experimentally and well documented in the literature . Isomerization reaction mechanisms and spectroscopic studies of some oximes were also performed theoretically . Schiff bases are well‐known compounds and are commonly used in industrial and biological area as a reaction intermediate.…”