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.

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Photolysis of F2 and O2 suspended in solid N2, Ar, or O2 produces infrared absorptions of an oxyfluoride other than OF2 and O2F2. Isotopic labeling, concentration dependence, diffusion behavior, and normal coordinate analysis permit assignment of these bands, at 1499.7, 586.4, and 376.0 cm−1, to O2F. On diffusion at low temperatures, this molecule forms only loosely bound aggregates, (O2F)n, though it is a free radical. Normal coordinate analysis shows that the O–O bond of O2F is a double bond, like those in O2 and in O2F2 and that the OF bond is much weaker than those in OF2. Thus, O2F resembles O2F2 in its bonding.