Heteroarylcarbenes

Sheridan, Robert S.

doi:10.1021/cr400150a

Cited by 33 publications

(27 citation statements)

References 118 publications

(183 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The decomposition process could also be followed by attenuated total reflectioninfrared spectroscopy (ATR-IR) by observation of the disappearance of the distinctive C=N=N stretch of the starting diazo function. 36 Thus, neat diphenyl 1a and dimethoxy 1b exhibit stretches at 2034 and 2029 cm -1 , respectively, whilst diazofluorene 2 has two peaks at 2054 and 2084 cm -1 , and these clearly decreased during the curing process (Table 1, This study provided evidence for thermal or photo-initiated collapse of the diazo function at the polymer surface at rates consistent with the known reactivity of carbenes; [37][38][39][40] of interest now was an understanding of the nature of the polymer on the surface modification reaction, and to achieve this, a comparative study of reactions with PS beads, along with the low surface energy materials, medium density polyethylene (MDPE), low density polyethylene (LDPE) and ultra-high molecular weight polyethylene (UHMWPE) using 4,4'-(diazomethylene)bis(N,N-dimethylaniline)…”

Section: Resultsmentioning

confidence: 54%

A comparative study of diaryl carbene insertion reactions at polymer surfaces

Iqbal

Lui

Moloney

et al. 2019

Applied Surface Science

View full text Add to dashboard Cite

A detailed investigation of the reactions of diaryldiazo compounds for the surface modification of several polymers has been conducted. This has revealed that the rate of reaction of diaryldiazo compounds is influenced by their substituents, that the reaction is exothermic, and that the polymer itself exerts an influence on the surface modification. The results are consistent with the formation and insertion of a carbene intermediate at the polymer surface. It was further shown that such surface modified polymers, characterized using surface sensitive techniques, display macroscopic behavior consistent with the presence of the newly introduced surface chemical functionality, characterized using a combination of surface sensitive and bulk analytical techniques. This approach is complementary to directed energy deposition approaches, offers an alternative route to functional polymers, and provide a direct link between surface chemistry and observable macroscopic properties.

show abstract

Section: Resultsmentioning

confidence: 54%

A comparative study of diaryl carbene insertion reactions at polymer surfaces

Iqbal

Lui

Moloney

et al. 2019

Applied Surface Science

View full text Add to dashboard Cite

show abstract

“…[32] We have investigated numerous aryl-and heteroaryldiazo compounds and the rearrangements of the carbenes formed from them [28,33] by flash vacuum pyrolysis (FVP) [34] or photolysis. [28,35] Thus, FVP of the sodium salts of benzaldehyde and tropone tosylhydrazones produced heptafulvalene arising from the dimerization of cycloheptatetraene (CHT) (Scheme 4). [36,37] Later, the triplet cycloheptatrienylidene (T) was observed by electron spin resonance (ESR) spectroscopy in the matrix photolysis of diazotropone, itself generated by FVP of the tosylhydrazone salt.…”

Section: þmentioning

confidence: 99%

Nitrogen- and Sulfur-Containing Energetic Compounds. 64 Years of Fascinating Chemistry

Wentrup¹

2019

Aust. J. Chem.

View full text Add to dashboard Cite

This essay details the author’s work with high-energy molecules based on sulfur or nitrogen, or both, which started with amateur rocket propellants like zinc dust and sulfur followed by experiments with the highly sensitive compounds nitrogen trichloride and fulminating gold. Research on the inorganic and organic fulminates and the isomeric cyanates led to detailed investigations of reactive intermediates generated by flash vacuum pyrolysis or photolysis, in particular nitrenes and carbenes derived from azides, diazo compounds, triazoles, and tetrazoles and characterized in low temperature matrices.

show abstract

“…[97] Da sich viele Heteroarylcarbene thermisch in Arylnitrene umlagern, ist es normalerweise nicht mçglich, EPR-Spektren von Heteroarylcarbenen bei Anwendung von FVP zu beobachten;s tattdessen werden die umgelagerten Arylnitrene gefunden [Gl. [98] Fluorsulfonylnitren, FSO 2 N, in seinem Triplett-Grundzustand wurde durch FVP von FSO 2 N 3 in einem 30 mm langen Quarzpyrolyserohr mit 1.0 mm i.D.b ei 800 8 8Cg eneriert und in einer Ar-Matrix isoliert;dies ermçglichte seine verlässliche Charakterisierung durch IR-und UV/Vis-Spektroskopie. [58] Heteroarylcarbene lassen sich jedoch mittels Matrixphotolyse beobachten.…”

Section: Epr- Ir-und Uv/vis-spektroskopieunclassified

“…[58] Heteroarylcarbene lassen sich jedoch mittels Matrixphotolyse beobachten. [98] Fluorsulfonylnitren, FSO 2 N, in seinem Triplett-Grundzustand wurde durch FVP von FSO 2 N 3 in einem 30 mm langen Quarzpyrolyserohr mit 1.0 mm i.D.b ei 800 8 8Cg eneriert und in einer Ar-Matrix isoliert;dies ermçglichte seine verlässliche Charakterisierung durch IR-und UV/Vis-Spektroskopie. [99] Das Fluorsulfonylradikal FSO 2 entstand ebenfalls und wurde als solches charakterisiert.…”

Section: Epr- Ir-und Uv/vis-spektroskopieunclassified

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Wentrup

2017

Angewandte Chemie

View full text Add to dashboard Cite

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.

show abstract

Heteroarylcarbenes

Cited by 33 publications

References 118 publications

A comparative study of diaryl carbene insertion reactions at polymer surfaces

A comparative study of diaryl carbene insertion reactions at polymer surfaces

Nitrogen- and Sulfur-Containing Energetic Compounds. 64 Years of Fascinating Chemistry

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Contact Info

Product

Resources

About