The Infrared Spectrum and Force Field of Matrix Isolated <i>cis</i>-Thionylimide (HNSO)

Tchir, Peter O.; Spratley, Richard D.

doi:10.1139/v75-324

Cited by 37 publications

(17 citation statements)

References 6 publications

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“…The production of cis-HNSO, the matrix isolation apparatus, and the infrared spectrometer (Perkin-Elmer 225) have been described previously (2). Photolysis was carried out using a 100 W PEK medium pressure mercury lamp (#112-2118) powered by a PEK model 401 power supply.…”

Section: Methodsmentioning

confidence: 99%

The Photolysis of Matrix Isolated cis-Thionylimide. 1. The Identification and Infrared Spectra of cis-HOSN, HSNO, and SNO

Tchir¹,

Spratley²

1975

Can. J. Chem.

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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.

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Section: Methodsmentioning

confidence: 99%

The Photolysis of Matrix Isolated cis-Thionylimide. 1. The Identification and Infrared Spectra of cis-HOSN, HSNO, and SNO

Tchir¹,

Spratley²

1975

Can. J. Chem.

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“…Therefore, the possibility that the 1190 cm-I band is due to the SNO-ion with this absorption assigned to the NO stretch has been considered. However, the low 15N shift makes this unlikely since the observed shift is 25 cm-' in the neutral SNO molecule (1).…”

Section: Torsionmentioning

confidence: 96%

“…If a period of this low energy photolysis was followed by higher energy photolysis (h > 2000 A), most of the absorptions grew rapidly (1). However, four of the weak absorption peaks decreased in intensity with this secondary photolysis.…”

Section: Trans-hnsomentioning

confidence: 99%

The Photolysis of Matrix Isolated cis-Thionylimide. 2. The Identification and Infrared Spectra of trans-HNSO and NSO

Tchir¹,

Spratley²

1975

Can. J. Chem.

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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]

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“…On the basis of the fact that no other products were detected in the presence of 91, it was suggested that a catalysis of the transformation of nitroso oxides to nitro compounds takes place in this system 128 . Perhaps the reaction is similar to an addition of carbonyl oxide to carbonyl group to form secondary ozonide (equation 19) 133 . Initially, the complex of nitroso oxide with dichloroacetone molecule is formed and reacts with the second ketone molecule to form an intermediate product of the type of secondary ozonide.…”

Section: E Reactions Of Nitroso Oxides With Organic Compoundsmentioning

confidence: 99%

The chemistry of nitroso oxides

Chainikova

Khursan

Safiullin

2014

Patai's Chemistry of Functional Groups

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Nitroso oxides (RNOO) are the isoelectronic analogs of carbonyl oxides (R 2 COO) and ozone (O 3 ) and, as well as these species, possess a three‐centered 4π‐electron system, which determines their chemical properties and reactivity unusual for a family of peroxides. The review is focused on the chemistry of the parent nitroso oxide (HNOO) and its aromatic analogs (ArNOO). The structure, spectral properties, methods for generation, reactivity and mechanisms of various transformations of these species both in the gas and condensed media are discussed in detail. An aromatic substituent significantly stabilizes the π‐system of nitroso oxide. The typical reactions of nitroso oxides are O‐transfer to an appropriate substrate or [3+2]‐cycloaddition to unsaturated bonds. Special attention was paid to the redox isomerization of arylnitroso oxides with ring cleavage that leads to the formation of diene nitrile oxides.

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The Infrared Spectrum and Force Field of Matrix Isolated cis-Thionylimide (HNSO)

Abstract: 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.

Cited by 37 publications

References 6 publications

The Photolysis of Matrix Isolated cis-Thionylimide. 1. The Identification and Infrared Spectra of cis-HOSN, HSNO, and SNO

The Photolysis of Matrix Isolated cis-Thionylimide. 1. The Identification and Infrared Spectra of cis-HOSN, HSNO, and SNO

The Photolysis of Matrix Isolated cis-Thionylimide. 2. The Identification and Infrared Spectra of trans-HNSO and NSO

The chemistry of nitroso oxides

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