Thermally Persistent Carbonyl Nitrene: FC(O)N

Carbenes and nitrenes can exist in both singlet and triplet states, sometimes equally stable and interconverting either thermally or photochemically. Many carbene and nitrene reactions proceed via tunneling at low temperatures. Numerous singlet and triplet states have been characterized spectroscopically, and a detailed understanding of the chemical and physical properties of carbenes and nitrenes is emerging. There has been significant progress in the direct observation of carbenes, nitrenes, and many other reactive intermediates in recent years through the application of matrix photolysis and flash vacuum pyrolysis linked with matrix isolation at cryogenic temperatures. Our understanding of singlet and triplet states has improved through the interplay of spectroscopy and computations. Bistable carbenes and nitrenes as well as many examples of tunneling have been discovered and numerous rearrangements and fragmentations have been documented. The correlation of the zero-field splitting parameter D with calculated spin densities on nitrenes and carbenes is discussed. This Minireview gives an overview of some of these developments.

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“…Eqs. (13) and (14)], [59][60][61] alkoxy-and aryloxycarbonylnitrenes [Eq. (15)], [62] and carbamoylnitrenes R 2 NÀCOÀN [Eq.…”

Section: Triplet and Singlet Acylnitrenes (Oxazirines)mentioning

confidence: 99%

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry

Wentrup

2018

Angew Chem Int Ed

127

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“…25 kcal mol À1 . [105] Sogar Cyancarben, HCCN,w urde durch FVP von Azidoacetylen bei ungefähr 270 8 8Cgeneriert und in einer Ar-Matrix isoliert. [104] FVP von Fluorcarbonylazid, FCON 3 ,b ei 700 8 8Cm it Isolierung des Produkts in einer Argonmatrix ermçglichte die Isolierung und IR-spektroskopische Charakterisierung von Tr iplett-Fluorcarbonylnitren, FCON,einem seltenen Beispiel eines thermisch generierten, beobachtbaren Carbonylnitrens.…”

Section: Angewandte Chemieunclassified

“…(25)]. [105] Sogar Cyancarben, HCCN,w urde durch FVP von Azidoacetylen bei ungefähr 270 8 8Cgeneriert und in einer Ar-Matrix isoliert. Es wurde ebenfalls durch Matrixphotolyse erhalten, isomerisiert aber unter photolytischen Bedingungen zu Isocyancarben und cyclischem HCCN.…”

Section: Angewandte Chemieunclassified

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Wentrup

2017

Angewandte Chemie

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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.

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“…Wu CO (e), [8] FNCO (f), [18] CF 2 (g), [19] FSNCO (h), [20] and F 2 CO (not shown in Figure 1) [21] were also identified. Wu CO (e), [8] FNCO (f), [18] CF 2 (g), [19] FSNCO (h), [20] and F 2 CO (not shown in Figure 1) [21] were also identified.…”

mentioning

confidence: 92%

“…[*] Z. Wu CO (e), [8] FNCO (f), [18] CF 2 (g), [19] FSNCO (h), [20] and F 2 CO (not shown in Figure 1) [21] were also identified. Given the predominant formation of CF 3 in the unimolecular decomposition of CF 3 S(O)NCO in the highly diluted Ar and N 2 mixture (1:1000), the most likely carrier for the IR band of 2237.6 cm À1 should belong to the rest part of the precursor,OCNSO.T oaid the assignment, quantum chemical calculations on the IR spectra of OCNSO have been performed and the results are summarized in Table 1.…”

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confidence: 99%

Heterocumulene Sulfinyl Radical OCNSO

Liu

et al. 2017

Angewandte Chemie

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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.

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Thermally Persistent Carbonyl Nitrene: FC(O)N

Cited by 27 publications

References 41 publications

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Heterocumulene Sulfinyl Radical OCNSO

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