PETER 0. TCHIR and RICHARD D. SPRATLEY. Can. J. Chem. 53,2331Chem. 53, (1975.It is shown that the low energy (h > 3000 A) photolysis of cis-HNSO in an argon matrix leads to formation of trans-HNSO. Four i.r. absorptions are observed and assigned for trans-HNSO and an approximate partial force field is calculated using data from isotopic substitutions. A comparison is made of the i.r. spectra of cis-and trans-HNSO using the intramolecular hydrogen bond of the cis form as a basis for explanation of the differences. Photolysis of cis-HNSO in argon matrices using vacuum U.V. light (1216 A) has resulted in a single i.r. absorption at 1195 cm-I which has been assigned to the radical, NSO. [Traduit par le journal]

PETER 0 . TCHIR and RICHARD D. SPRATLEY. Can. J . Chem. 53,2318Chem. 53, (1975. cis-HNSO has been photolyzed in argon matrices using a medium pressure mercury lamp. Examination of the infrared spectra has revealed the presence of four photolysis products. With the aid of isotopic substitution these species have been identfied as cis-HOSN, cis-HSNO, trans-HSNO, and SNO, all previously unknown. Assignments have been made for a11 four products and force fields calculated for cis-HOSN and trans-HSNO. The following reaction scheme has been postulated for the photolysis induced process: cis-HNSO -+ cis-HOSN -+ cis-HSNO + trans-HSNO -+ SNO. The extent of this reaction sequence has been found to depend on reaction time and photolysis energy. IntroductionIn the ultraviolet spectrum of cis-HNSO only one diffuse absorption and one continuum were observed (1). From this observation it was deduced that photolysis of the molecule was occurring. Since it was possible that the hydrogen was being removed to give the NSO radical, this photolysis appeared to be an ideal system for a study utilizing the matrix isolation technique. In this technique a hydrogen atom can diffuse away through the matrix to leave behind the isolated, stabilized radical. On the other hand, if the product or products were unstable isomers of cis-HNSO, they might also be stabilized at the low temperature of the matrix.In this paper we describe the results of the mercury arc photolysis of cis-HNSO in argon matrices: in part I the infrared results are presented and four new molecular species are identified; in part I1 the reactions taking place in the matrix are considered.

Infrared spectra of cis-HNSO and several deuterium, 15N, and 34S isotopically substituted homologs have been obtained in argon and nitrogen matrices. The Fermi resonance between ν4 and 2ν5 is discussed. A force field has been calculated.

Raman spectra of O, F, in CCIF, solution are reported for the first time. A vibrational assignment is proposed based on polarisation data. A reinvestigation of the vibrational-potential function and a calculation of the barrier height to internal rotation have been made. THE i.r. spectrum of 02F2 was first observed using matrix-isolation techniques by Brown,l by Spratley et aZ.,, and by Arkell,3 the latter two groups of workers being primarily concerned with the i.r. spectrum of 0,F. None of these workers, however, observed the complete spectrum of 02F,. Loos et aL4 have recorded the complete i.r. spectrum of solid 02F2 and, in an earlier paper,5 we reported the solid-state i.r. and Raman spectra and also the i.r. spectrum of 02F2 trapped in various matrices at 20 K. Noble6 has carried out a normal-co-ordinate analysis of 0,F and Loos et aL4 have undertaken one for 02F2 using these solid-state i.r. frequencies.This paper describes Raman polarisation studies on 0,F2 dissolved in CClF, at about 190 K. This work was mentioned in proof in a previous publication5 and confirms an assignment of lower-frequency modes given therein which differs slightly from that of Loos et aL4 Using this assignment, and solution-phase frequencies, we have reinvestigated the vibrational-potential function of this unusual molecule. EXPERIMENTAL

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