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Elusive Fluoro Sulfinyl Nitrite, FS(O)NO, Produced by Photolysis of Matrix‐isolated FS(O) 2 N
Author(s) -
Zeng Xiaoqing,
Beckers Helmut,
Neuhaus Patrik,
Grote Dirk,
Sander Wolfram
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100396
Subject(s) - nitrene , photodissociation , intersystem crossing , chemistry , photochemistry , singlet state , electron paramagnetic resonance , matrix isolation , nitrite , thermal decomposition , infrared spectroscopy , excited state , nuclear magnetic resonance , physics , atomic physics , organic chemistry , nitrate , catalysis
Triplet fluoro sulfonyl nitrene, FS(O) 2 N ( X 3 A") was generated by ArF excimer laser irradiation ( λ = 193 nm) of FS(O) 2 N 3 isolated in solid noble gas matrices. The novel nitrene was characterized by IR ( 15 N‐, 18 O‐, and 34 S‐labeling), UV/Vis, and EPR spectroscopy. The elusive sulfinyl nitrite, FS(O)NO, was formed in a spin‐forbidden reaction upon photolysis ( λ > 320 nm) of triplet FS(O) 2 N. Triplet‐singlet intersystem crossing (ISC) was found to compete with a spin‐allowed fragmentation of the sulfonyl nitrene, which yields SO 2 + FN ( 3 Σ – ) and FNO + SO ( 3 Σ – ). Guided by DFT calculations the complex photo‐decomposition of FS(O) 2 N ( X 3 A") is discussed.