Isolierung labiler NSO‐Pseudohalogen‐Spezies

Labbow, René; Michalik, Dirk; Reiß, Fabian; Schulz, Axel; Villinger, Alexander

doi:10.1002/ange.201601878

Cited by 21 publications

(2 citation statements)

References 45 publications

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“…This is attributed to substituent exchange between a quaternary silane and a silylium ion. 22 23 24 25 Such dealkylation of quaternary silanes has been independently studied by us. 26…”

Section: Skeletal Rearrangements Of Vinylcyclopropanes Involving Cycl...mentioning

confidence: 99%

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Skeletal Rearrangements Involving Cyclopropyl- and Alkene-Stabilized Silylium Ions

Long,

He,

Klare

et al. 2023

Synlett

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This Account summarizes the fascinating chemistry of cyclopropyl-stabilized silylium ions which are readily available from vinylcyclopropanes (VCPs). Depending on the nucleophilic partner, these reactive intermediates undergo either direct ring opening or ring expansion to nonclassical alkene-stabilized silylium ions. The latter can also be accessed by gold- as well as proton electrophiles from silicon compounds containing unsaturated C–C bonds. All of these reaction cascades can be terminated by C–H or C–C as well as Si–O bond formation. From this, a clearer picture of the versatility of these rather complex chemistry emerges.

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“…This is attributed to substituent exchange between a quaternary silane and a silylium ion. 22 23 24 25 Such dealkylation of quaternary silanes has been independently studied by us. 26…”

Section: Skeletal Rearrangements Of Vinylcyclopropanes Involving Cycl...mentioning

confidence: 99%

“…Dealkylation and dearylation at the silicon atom were involved when tertiary hydrosilanes 6b – d were used instead of secondary hydrosilane 6a , again arising from substituent redistribution. 22 23 24 25 26…”

Section: Skeletal Rearrangements Of Vinylcyclopropanes Involving Cycl...mentioning

confidence: 99%

Skeletal Rearrangements Involving Cyclopropyl- and Alkene-Stabilized Silylium Ions

Long,

He,

Klare

et al. 2023

Synlett

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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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HPCO—A Phosphorus‐Containing Analogue of Isocyanic Acid

et al. 2017

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We describe the isolation and spectroscopic characterization of the heavier phosphorus-containing analogue of isocyanic acid (HPCO), and its isotopologue (DPCO). This fundamental small molecule,which has been postulated to exist in interstellar space,has thus far only been observed at low gas phase concentrations or in inert gas matrices.Inthis report we describe its synthesis,spectroscopic properties,and reactivity in solution. In1830,WçhlerandLiebiginvestigatedcyanicacid(HOCN)and its reactivity towards ammonia in an effort to synthesize ammonium cyanate,w hich was found to afford urea on mild heating.[1] Given the technological limitations at the time, very little was deduced about the constitution of the species studied. However these discoveries were fundamental in defining the concept of isomerism, for example,t he authors discovered that the silver salts of cyanate and fulminate have the same composition. Historic interest in such simple acids has largely focused on fulminic acid (and salts of its conjugate base) in large part due to its explosive properties. [2,3] The molecular structures of isocyanic (HNCO) and fulminic acid (HCNO), were not determined until 1950 by Herzberg and Reid, [4] and 1966 by Beck, respectively.[5] Nowadays,spectroscopic evidence for all four isomeric species isocyanic acid, [6] cyanic acid, [7] fulminic acid, [5] and isofulminic acid is available (Scheme 1).[8] HNCO, [9] HOCN, [10] and HCNO have even been detected in interstellar space. [11] In contrast, analytical data for the heavier phosphoruscontaining homologues HPCO are scarce.Several reports by Matveev claim to have synthesized HOCP from phosphaalkyne precursors, [12,13] however these studies were found to not be reproducible by the group of Becker and others. [14] Becker and co-workers suggested the existence of HOCP after protonation of the 2-phosphaethynolate anion, PCO À , [14,15] but clearly emphasized that this hypothesis was doubtful because the compound could neither be isolated nor further characterized. [16] Numerous theoretical studies have focused on the different isomers of the HPCO system, predicting HPCO to be 23 kcal mol À1 more stable than HOCP,w ith an activation barrier for interconversion of 70 kcal mol À1 . [17][18][19][20][21][22] These computational studies have stimulated further research, indicating that HPCO might be stable in interstellar space.All successful experimental HPCO studies thus far have tried to mimic interstellar conditions,such as low gas-phase concentration of HPCO or the use of noble gas matrices.T hus,t here are two studies of the generation of HPCO by gas discharges of highly dilute PH 3 /CO mixtures (in He or Ar), which allowed the recording of infrared [23] and microwave spectra of HPCO. [24,25] These studies have corroborated the presence of HPCO and not the isomeric HOCP.M ore recently,H PCO has been proposed as an intermediate in the formation of phosphinecarboxamides and phosphinidene-carbene adducts in the reaction of PCO À with ammonium and imidazolium salts, ...

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Isolierung labiler NSO‐Pseudohalogen‐Spezies

Cited by 21 publications

References 45 publications

Skeletal Rearrangements Involving Cyclopropyl- and Alkene-Stabilized Silylium Ions

Skeletal Rearrangements Involving Cyclopropyl- and Alkene-Stabilized Silylium Ions

Heterocumulene Sulfinyl Radical OCNSO

HPCO—A Phosphorus‐Containing Analogue of Isocyanic Acid

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