REACTIONS OF LASER-ABLATED CHROMIUM ATOMS WITH NITRIC OXIDE MOLECULES: INFRARED SPECTRA OF $NCrO, Cr-\eta^{1}-(NO)_{z} (x=1,2,3,4)$ AND $Cr-\eta^{2}$-NO IN SOLID ARGON
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Date
1998
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Ohio State University
Abstract
Laser-ablated chromium atoms have been reacted with NO molecules during condensation in excess argon. Absorptions due to NCrO $(976.1, 866.2 cm^{-1}), Cr-\eta^{1}-NO (1614.3, 541.1 cm^{-1})$ and $Cr-\eta^{2}-NO (1108.8, 528.2, 478.0 cm^{-1})$ are observed and identified via isotopic substitutions and DFT calculations. Formation of the more stable NCrO insertion product requires activation energy, while $Cr-\eta^{1}-NO$ and $Cr-\eta^{2}-NO$ can be formed on diffusion of cold reagents in solid argon. High nitrosyls are also formed on annealing. Based on the observation of mixed isotopic multiplets, a $1623.3 cm^{-1}$ absorption is assigned to $Cr-\eta^{1}(NO)_{2}$, a $1663.5 cm^{-1}$ absorption to $Cr-\eta^{1}-(NO)_{3}$, and absorptions at 1726.0, 633.0 and $506.1 cm^{-1}$ are assigned to $Cr-\eta^{1}-(NO)_{4}$.
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Author Institution: Department of Chemistry, University of Virginia