Electronic spectrum of jet-cooled phenyl nitrene

Ozawa, K; Ishida, Tohru; Fuke, Kiyokazu; Kaya, Kunimitsu

doi:10.1016/0009-2614(88)80036-8

Cited by 16 publications

(5 citation statements)

References 18 publications

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“…In 1966, Reiser et al reported the first electronic spectrum of PhN [1] and their studies were extended by subsequent researchers [2][3][4]. Porter and Ward assigned a UV absorption band of triplet PhN in 1968, which was supported by other groups [5,6,12]. In 1990, Hayes and Sheridan measured the vibrational frequencies of PhN from a mixture of PhN and dehydrozaepine [13].…”

Section: Introductionmentioning

confidence: 96%

“…Experimental and theoretical studies of phenylnitrene (PhN) have been subjects of great interest to both organic and physical chemists over the past 40 years [1][2][3][4][5][6] because of its useful synthetic and industrial applications [7]. PhN is a diradical with C 2v symmetry, which is generally produced by pyrolysis or photolysis of phenyl azide [1,[7][8][9].…”

Section: Introductionmentioning

confidence: 99%

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Identification and Chemistry of Phenylnitrene in Premixed Pyridine/Oxygen/Argon Flame with Tunable Synchrotron Photoionization

Tian

Yuan

Wang

et al. 2007

Chinese Journal of Chemical Physics

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The triplet state phenylnitrene (PhN) species generated from the low-pressure (4.0 kPa) premixed laminar pyridine/oxygen/argon flame was detected and identified using tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry techniques. The ionization energies of PhN were determined experimentally by photoionization efficiency spectra and theoretically by calculations. The results indicate that PhN has a 3 A 2 ground state and its first and second adiabatic ionization energies are 8.04 and 9.15±0.05 eV, respectively. Furthermore, the formation and consumption pathways of PhN are proposed according to the species detected in the present work. PhN is the first nitrogen-containing diradical detected in combustion chemistry, and so it should be added to the kinetic model of pyridine flames.

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Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Identification and Chemistry of Phenylnitrene in Premixed Pyridine/Oxygen/Argon Flame with Tunable Synchrotron Photoionization

Tian

Yuan

Wang

et al. 2007

Chinese Journal of Chemical Physics

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“…Its formation is not inÑuenced by oxygen. The characteristic absorption of is Br 2 ~õbserved by irradiation of 3-BrA in the presence of Br~ (5 ] 10~3 M). The solvated electron and the long-lived halogenoanilino radical cations are detected.…”

mentioning

confidence: 99%

Mechanism of 3-halogenoaniline photolysis in methanol

Othmen¹,

Boule²,

Richard³

1999

New J. Chem.

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“…Note that triplet phenylnitrene is the ground state of this molecule and is thus more stable than the singlet. [32][33][34][35][36][37][38][39][40] According to our calculations the difference is 8.5 kcal/mol.…”

Section: A Co Elimination Following Ring Contraction (R) Parts I and ...mentioning

confidence: 74%

Decomposition of Anthranil. Single Pulse Shock-Tube Experiments, Potential Energy Surfaces and Multiwell Transition-State Calculations. The Role of Intersystem Crossing

et al. 2006

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The thermal decomposition of anthranil diluted in argon was studied behind reflected shock waves in a 2 in. i.d. pressurized driver single-pulse shock tube over the temperature range 825-1000 K and overall densities of approximately 3 x 10(-5) mol/cm(3). Two major products: aniline and cyclopentadiene carbonitrile (accompanied by carbon monoxide) and four minor products resulting from the decomposition were found in the postshock samples. They were, in order of decreasing abundance, pyridine, CH(2)=CHCN, HCN and CHC-CN, and comprised only a few percents of the overall product distribution. Quantum chemical calculations were carried out to determine the sequence of the unimolecular reactions that lead to the formation of cyclopentadiene carbonitrile and of phenylnitrene/phenylimine that are the precursors of aniline. They form aniline by reactions with traces of water impurities. To produce cyclopentadiene carbonitrile, two main processes must take place: CO elimination and ring contraction from a six- to a five-membered ring. It was shown that this can occur via two parallel pathways where CO elimination takes place prior to or following ring contraction. Singlet potential energy surfaces for all the elementary reactions that lead to the formation of cyclopentadiene carbonitrile and phenylnitrene/phenylimine were obtained. Their rate constants were calculated on the basis of the results of the quantum chemical calculations using transition-state theory. A kinetic scheme containing these reactions was constructed and multiwell calculations were performed to evaluate the mole percent of the products as a function of temperature. A very serious disagreement between the experimental results and the results of calculations showed that the singlet PESs could not account for the observed experimental rates. No other singlet PESs that lead to the formation of these products could be found. In view of this observation, attempts to find pathways that lead to the formation of cyclopentadiene carbonitrile and phenylnitrene/phenylimine on triplet surfaces were made. Such surfaces were found, and singlet <--> triplet intersystem crossing probabilities and crossing rate constants were calculated as well as the rate constants of all the elementary steps on the triplet surfaces. A reaction scheme was constructed and multiwell calculations were performed, including also the pathways on the singlet surfaces, to evaluate the mole percent of the products as a function of temperature. The agreement between the experimental results and these calculations was quite satisfactory.

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Electronic spectrum of jet-cooled phenyl nitrene

Cited by 16 publications

References 18 publications

Identification and Chemistry of Phenylnitrene in Premixed Pyridine/Oxygen/Argon Flame with Tunable Synchrotron Photoionization

Identification and Chemistry of Phenylnitrene in Premixed Pyridine/Oxygen/Argon Flame with Tunable Synchrotron Photoionization

Mechanism of 3-halogenoaniline photolysis in methanol

Decomposition of Anthranil. Single Pulse Shock-Tube Experiments, Potential Energy Surfaces and Multiwell Transition-State Calculations. The Role of Intersystem Crossing

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