Chemistry of trifluoroamine oxide. VI. Formation of trifluoroamine oxide in the fluorine-nitric oxide flame

Abstract

methyl resonance (not shown) is a doublet at 1.37 ppm vs. DSS and has a spacing of 6.0 Hz. Of the three protons remaining on the propylenediamine backbone, it appears that Ha produces the triplet-like resonance at highest field, and that Hb and Hc are almost coincident at lowest field. The triplet-like resonance of Ha results from spin coupling to Hb and Hc with nearly equal magnitudes (/ab « -12.5 and /ac 11.0 Hz).6•7Simultaneous irradiation of cobalt-59 and the methyl doublet leads to changes in the low-field portion of Figure 2B which are consistent with the assignment of Hc. The approximate chemical shifts are ¿a ~2.48, ¿b ~2.93, and ¿c ~3.05 ppm vs. DSS. Use of solvent shifts and a higher spectrometer frequency spreads out the spectrum sufficiently for a complete analysis, now in progress.The sharpness of the Ha lines compared to the Hb lines tends to indicate that the Co-N-C-H coupling constant is greater for equatorial protons than for axial protons. A similar result is evident for Co(en)31 23+ in Figure 1C.21 This finding, in addition to the fact that ¿b > Sa in L-[Co(( -)pn)3]3+ supports the assignment of ¿axia¡ <~2.75 ppm and ¿equatorial ~2.93 ppm in Co(en)33+.

Infrared spectroscopic evidence for nitrogen hypofluorite, an isomer of nitrosyl fluoride, in inert gas matrixes

“…The absence of the intense ir fundamentals of F3NO, except slight traces at the higher F2:NO ratios, suggests that postulated species such as F2N0 22 are not present in any appreciable concentration under the experimental conditions employed. This observation, in addition to the appearance of the three infrared absorptions at 1886.6, 735.1, and 492.2 cm-1 (Ar matrix) in highly dilute matrices at low F2 :NO ratios, lends further credence to the postulated existence of nitrogen hypofluorite, NOF.…”

Infrared and EPR Spectra of the Difluoronitroxide Radical

“…The geometry and electronic structure of the F 2 NO radical has been the subject of intense study by quantum chemical methods. , More than 20 years ago, Smardzewski and Fox suggested that this radical might be formed as an intermediate in a series of sequential addition reactions of F atoms with NO Although this scheme was used successfully to synthesize F 3 NO, attempts to detect the intermediate F 2 NO in mixtures of F 2 and NO in the gas phase and in solids were unsuccessful . This is presumably because reaction 2 is nearly thermoneutral, and therefore F 2 NO is present only in small concentrations, particularly at elevated temperatures.…”

Modern applications of matrix isolation technique to investigation of radical species generated in atom–molecular chemical reactions

“…Fox et al 148,149 postulated the formation of a radical species F 2 NO . in the synthesis of F 3 NO molecules…”