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Matrix Isolation and Density Functional Theory Study of Bis(trifluoromethyl)dioxodiazine: A Photodimer of Trifluoronitrosomethane

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Brendan C. Haynie,^† Megan J. Morgan,^‡ and Christopher A. Baumann*

Department of Chemistry, University of Scranton, Scranton, Pennsylvania 18510-4626

J. Phys. Chem. A, 2005, 109 (24), pp 5307–5315

DOI: 10.1021/jp050730z

Publication Date (Web): May 26, 2005

Section:

Physical Organic Chemistry

Abstract

Trifluoronitrosomethane (CF₃NO) was trapped in rare gas matrixes and irradiated at 633 and 670 nm. The infrared spectra of the postirradiation samples exhibit features consistent with cis and trans conformers of bis(trifluoromethyl)dioxodiazine, a previously uncharacterized species. The concentration dependence of the formation of the dimer is consistent with a mechanism in which monomers trapped in adjacent sites undergo excitation and subsequent reaction. The dimers reversibly form the monomer when irradiated with ultraviolet light. Density functional theory was used to determine the structure of the dimers and predict their infrared and Raman spectra. The predicted vibrational frequencies are in agreement with those observed. A third (skewed) conformation was predicted to have a triplet ground state, but no evidence of this species was observed. All three dimers exhibit significant diradical character, as evidenced by comparatively low N−N and high N−O stretching frequencies. Transition-state calculations predict the dimerization barrier to range from 17.1 (cis) to 35.0 (trans) kJ mol^-1 for the singlet dimers and to be 62.1 kJ mol^-1 for the triplet dimer. This is an example of nitroso dimerization that requires electronic excitation to proceed.