The Missing Link: Triplet Fluorocarbonyl Nitrene FC(O) N

作者：Zeng Xiaoqing; Beckers Helmut^*; Willner Helge; Grote Dirk; Sander Wolfram

来源：Chemistry - A European Journal, 2011, 17(14): 3977-3984.

DOI：10.1002/chem.201002955

• matrix isolation
• nitrenes
• photochemistry
• spectroscopic methods

The elusive triplet fluorocarbonyl nitrene, FC(O)N (X(3)A ''), has been generated in high yield from matrix-isolated FC(O)N-3 by ArF excimer laser photolysis (lambda = 193 nm). As a side product FNCO was formed. The novel nitrene was characterized by IR, UV/Vis, EPR spectroscopy, and quantum-chemical calculations. All six fundamental vibrations of FC(O) N at 1681.3, 1193.8, 879.8, 646.5, 588.7, and 434.8 cm(-1) (argon matrix, 16 K), their C-12/13, O-16/18, and N-14/15 isotopic shifts, and four electronic transitions at T-0 = 13 890, 25 428, 29 166, and 30 900 cm(-1) that exhibit vibrational fine structures have been detected. Under visible-light irradiation at lambda >= 495 nm, FC(O) N reacted with molecular N-2 in the matrix cage at 6 K to give back FC(O) N3, whereas near-UV irradiation at lambda >= 335 nm yielded FNCO. The singlet-triplet energy gaps of different carbonyl nitrenes are discussed.

• 出版日期2011-3