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Isomerizations between Nitrosyl Halides X−N=O and Isonitrosyl Halides X−O−N: A Matrix‐Spectroscopic Study
Author(s) -
Maier Günther,
Reisenauer Hans Peter,
De Marco Michael
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(20000303)6:5<800::aid-chem800>3.0.co;2-7
Subject(s) - halide , bromide , fluoride , chloride , matrix (chemical analysis) , irradiation , chemistry , photochemistry , matrix isolation , argon , inorganic chemistry , physics , organic chemistry , chromatography , nuclear physics
Irradiation of nitrosyl bromide BrNO ( 4 ) with light of the wavelength λ =248 nm and nitrosyl chloride ClNO ( 6 ) with λ =193 nm in an argon matrix at 10 K leads to the corresponding isomers isonitrosyl bromide BrON ( 5 ) and isonitrosyl chloride ClON ( 7 ). Both new compounds 5 and 7 have been identified by comparison of the experimental and calculated (BLYP/6‐311+G*) IR spectra. Nitrosyl fluoride FNO ( 8 ) could not be transferred into isonitrosyl fluoride FON ( 9 ). The back reactions 5 → 4 and 7 → 6 can be initiated by UV ( λ >310 nm), visible or IR light. The retransformation also occurs spontaneously in the matrix at 10 K under exclusion of any UV/UV or IR radiation. Surprisingly, the reaction rates of these spontaneous back reactions are temperature independent between 8.5 and 25 K. The mechanism of these processes is discussed.