Gas‐Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN

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Neutral five-atomic cumulenes formally consisting of two pseudohalogens (e.g.,NCO,NNN,NSO) by sharing the central nitrogen atom are exotic species that have been barely studied. Through flash vacuum pyrolysis of CF 3 S(O)NCO at ca. 1200 K, sulfinyl isocyanate,bearing resonance structures of O=CÀN=S=Oa nd O=C=NÀS=O, has been generated in the gas phase and subsequently characterized in cryogenic matrices (Ar and N 2 ). Its reversible conformational (syn and anti) interconversion and photodecomposition were observed.Smallinorganicmoleculesbearingmultiple-bondingC, O, S, Na toms are of astrochemical and biological relevance that have been the targets of numerous experimental and theoretical studies. [1] Particularly,s imple species consisting of the triatomic pseudohalogens NNN and NCO are of fundamental importance due to interesting structural, conformational, and bonding properties.F or instances,t he exotic high-energy polynitrogen species N 4 , [2] N 5 , [3] N 6 , [4] and their respective isoelectronic analogues NNCO, [5] OCNCO, [6] and OCNNCO [7] /OCNNNN [8] have attracted great interest in the recent few decades.D espite the challenges facing the synthesis and characterization due to the metastability and the lack of synthetic method, significant progress has been made in the generation and direct observation of the four-and six-atomic species with various spectroscopic techniques. However,t he existence of the five-atomic cumulene species (N 5 and OCNCO) has not yet been proved experimentally, although the salts of the cations N 5 +[9] and OCNCO + , [10] as well as the one-electron-less interpseudohalogen NCNCO/ NCCNO [11] have been synthesized and structurally characterized.

Heterocumulene Sulfinyl Radical OCNSO

Liu

et al. 2017

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Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Wentrup

2017

Die Anfänge der Flash‐Vakuumpyrolyse (FVP) ergaben sich in den 1940er und 1950er Jahren hauptsächlich aus dem massenspektrometrischen Nachweis pyrolytisch entstandener freier Radikale. In den 1960er Jahren begannen Organiker mit der Durchführung von FVP‐Experimenten zum Zweck der Isolierung neuer und interessanter Verbindungen und zum Verständnis pyrolytischer Prozesse. Seitdem wurden viele unterschiedliche Typen von Apparaten und Techniken entwickelt. Zielsetzung dieses Aufsatzes ist es, die wichtigsten Methoden vorzustellen wie auch eine Übersicht über typische Reaktionen und Beobachtungen zu geben, die mit den verschiedenen Techniken erreicht werden können. Dies umfasst unter anderem präparative FVP, chemische Abfangreaktionen, Matrixisolierung sowie Tieftemperatur‐Spektroskopie reaktiver Intermediate und instabiler Moleküle. Darüber hinaus ist die Kombination von FVP mit Matrixisolierung und Photochemie ein wirkungsvolles Instrument für Untersuchungen von Reaktionsmechanismen.

Spectroscopic Identification of H₂NSO and syn‐ and anti‐HNSOH Radicals

Dong

Deng

et al. 2018

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The simplest aminosulfinyl radical H 2 NSO has been generated in the gas phase through flash vacuum pyrolysis of CF 3 S(O)NH 2 at approximately 1000 K. Upon UV light irradiation (365 nm), 1,3-H migration occurs in H 2 NSO and furnishes an elusive N-amidyl radical HNSOH in syn and anti conformations in cryogenic matrices (N 2 or Ar,1 5K). Further 266 nm laser irradiation results in dissociation of HNSOH to H 2 Oa nd SN and concomitant reformation of H 2 NSO in trace amount. The identification of H 2 NSO,s yn-HNSOH, and anti-HNSOH by matrix-isolation IR spectroscopyi ss upported by high-level quantum chemical computations.