FBC-Anorganische Chemie, Bergische Universität Wuppertal, Wuppertal, Germany.
Chemistry. 2011 Mar 28;17(14):3977-84. doi: 10.1002/chem.201002955. Epub 2011 Mar 7.
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 (λ=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 (12/13)C, (16/18)O, and (14/15)N 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 λ≥495 nm, FC(O)N reacted with molecular N(2) in the matrix cage at 6 K to give back FC(O)N(3), whereas near-UV irradiation at λ≥335 nm yielded FNCO. The singlet-triplet energy gaps of different carbonyl nitrenes are discussed.
难以捉摸的三氟甲酰基氮烯，FC(O)N（X(3 A''），已经通过 ArF 准分子激光光解（λ=193nm）从基质隔离的 FC(O)N(3)中以高产率生成。作为副产物形成了 FNCO。这种新的氮烯通过红外、紫外/可见、电子顺磁共振波谱和量子化学计算进行了表征。在 1681.3、1193.8、879.8、646.5、588.7 和 434.8cm(-1)（氩基质，16K）下检测到 FC(O)N 的所有六个基本振动，其（12/13）C、（16/18）O 和（14/15）N 同位素位移，以及四个在 T(0)=13890、25428、29166 和 30900cm(-1) 的电子跃迁，这些跃迁表现出振动精细结构。在 λ≥495nm 的可见光照射下，FC(O)N 在 6K 下与基质笼中的分子 N(2)反应，重新生成 FC(O)N(3)，而近紫外光照射（λ≥335nm）则生成 FNCO。讨论了不同羰基氮烯的单重态-三重态能隙。
