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Fascinating Diazirinone: A Violet Gas
Author(s) -
Zeng Xiaoqing,
Beckers Helmut,
Willner Helge,
Stanton John F.
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200337
Subject(s) - chemistry , raman spectroscopy , irradiation , infrared spectroscopy , spectroscopy , analytical chemistry (journal) , infrared , yield (engineering) , photochemistry , noble gas , photodissociation , evaporation , absorption spectroscopy , matrix isolation , visible spectrum , absorption (acoustics) , organic chemistry , physics , materials science , optoelectronics , quantum mechanics , nuclear physics , acoustics , optics , metallurgy , thermodynamics
Diazirinone (cyclic N 2 CO) recently identified in solid noble gas matrices and in the gas phase by infrared spectroscopy, has now been trapped at –196 °C as a neat brownish‐yellow solid, and characterized by low‐temperature IR and Raman spectroscopy. Evaporation of the solid yields violet gaseous N 2 CO, which is surprisingly stable in a clean quartz cell. Its decay at room temperature in the dark follows a second‐order rate law ( k 2 = 4.9 × 10 –2 L mol –1 s –1 ) with a half‐life of 30 h at an initial pressure of 5 mbar. The visible absorption spectrum of the gas reveals a structured band with the 0–0 transition at 567 nm (17651 cm –1 ), and its assignment has been made with the aid of theoretical calculations. Cyclic diazirinone that is isolated in solid Ar at 16 K decomposes upon visible light irradiation to yield N 2 and CO, but after being exposed to ArF excimer laser irradiation (193 nm) the N=N bond is cleaved and the open‐chain isomers NOCN, ONCN, and ONNC are formed.