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Combination of LFP‐TRIR spectroscopy and DFT computation as a tool to determine the intermediate during the photooxidation of triarylphosphine
Author(s) -
Yasui Shinro,
Badal Md. Mizanur Rahman,
Kobayashi Shinjiro,
Mishima Masaaki
Publication year - 2014
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3383
Subject(s) - chemistry , microsecond , photochemistry , flash photolysis , phosphine , infrared spectroscopy , density functional theory , ultrafast laser spectroscopy , spectroscopy , infrared , millisecond , dichloromethane , computational chemistry , reaction rate constant , kinetics , organic chemistry , optics , physics , quantum mechanics , astronomy , solvent , catalysis
Laser flash photolysis‐time‐resolved infrared spectroscopy (LFP‐TRIR) was performed on an acetonitrile or dichloromethane solution of triarylphosphines, Ar 3 P, in air. A transient spectrum consisting of several absorption bands appeared in the region of 1050–1300 cm −1 on the TRIR on a microsecond timescale, which disappeared on a millisecond timescale. To identify the observed transient intermediate , the IR spectra of possible intermediates of the photoreaction were simulated by theoretical calculations based on density functional theory (DFT). The IR spectrum simulated for the phosphine peroxidic radical cation, Ar 3 P + OO • , well predicted the observed IR spectrum, showing that Ar 3 P + OO • is formed as a transient intermediate upon the LFP of Ar 3 P in air. Copyright © 2014 John Wiley & Sons, Ltd.