Please use this identifier to cite or link to this item: https://scholarbank.nus.edu.sg/handle/10635/94428
Title: O-Nitrosobis(trifluoromethyl)hydroxylamine: Unexpected conformational properties and an unusually long (CF3)2NO-NO bond. A combined study of the gaseous and solid states
Authors: How, G.A. 
Martin, F.K.
Whei, L.K.
View, W.L.
Mack, H.-G.
Mootz, D.
Poll, W.
Oberhammer, H.
Issue Date: 1993
Citation: How, G.A.,Martin, F.K.,Whei, L.K.,View, W.L.,Mack, H.-G.,Mootz, D.,Poll, W.,Oberhammer, H. (1993). O-Nitrosobis(trifluoromethyl)hydroxylamine: Unexpected conformational properties and an unusually long (CF3)2NO-NO bond. A combined study of the gaseous and solid states. Journal of the American Chemical Society 115 (15) : 6929-6933. ScholarBank@NUS Repository.
Abstract: The conformational properties and the geometric structure of gaseous O-nitrosobis(trifluoromethyl)-hydroxylamine, (CF3)2N-O-N=O, have been studied by infrared spectroscopy, electron diffraction, and ab initio calculations. From the relative intensities and band contours of the two N=O vibrations, a mixture of 80(10)% trans-syn and 20(10)% trans-anti conformers (ΔG = G(syn) - G(anti) = -0.8(3) kcal/mol) is derived (trans describes the orientation of the O-N bond relative to the CNC bisector and syn/anti refers to the orientation of N=O relative to N-O). Such a mixture of conformera with planar NONO groups is consistent with the electron diffraction intensities. In addition, the compound has been subjected to X-ray crystal structure analysis. In the solid state, only the trans-syn conformer is present. The O-N single bond is unusually long and differs strongly in the two phases: 1.572(21) Å in the gaseous state and 1.669(3) Å in the solid state. The results of ab initio calculations depend strongly on the calculational method, especially for the relative energy of the two conformera and for the O-N bond length: ΔE = E(syn)-E(anti) =-1.8, +0.6, and -3.3 kcal/mol and O-N =1.527, 1.401, and 1.717 Å with HF/3-21G,HF/6-31G*, and MP2/6-31G*, respectively. None of these predictions agrees very well with the experimental results for the gas phase.
Source Title: Journal of the American Chemical Society
URI: http://scholarbank.nus.edu.sg/handle/10635/94428
ISSN: 00027863
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

Page view(s)

137
checked on Mar 28, 2021

Google ScholarTM

Check


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.