Product Studies and Laser Flash Photolysis on Alkyl Radicals Containing Two Different β-Leaving Groups Are Consonant with the Formation of an Olefin Cation Radical

The behavior of the N,N-di(4-bromophenyl)nitrenium ion under acidic aqueous conditions was examined via laser flash photolysis experiments. A long-lived species forms and can be assigned as the cation radical or the dication. This species is unreactive towards nucleophiles and reactive towards strong electron donors, consistent with a cation radical. Mechanistic analysis indicates its formation is through a separate pathway than that of the nitrenium ion, suggestive of a triplet mechanism.

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SN1-type mechanism for the carbon-carbon bond cleavage of tetrakis(4-methylphenyl)ethanone cation radical. A laser flash photolysis study

Tetrahedron Letters ◽

10.1016/s0040-4039(00)74731-9 ◽

1992 ◽

Vol 33 (52) ◽

pp. 8105-8108 ◽

Cited By ~ 5

Author(s):

Ryoichi Akaba ◽

Masaki Kamata ◽

Hirochika Sakuragi ◽

Katsumi Tokumaru

Keyword(s):

Flash Photolysis ◽

Laser Flash Photolysis ◽

Bond Cleavage ◽

Cation Radical ◽

Laser Flash ◽

Carbon Bond ◽

Carbon Carbon Bond

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ChemInform Abstract: Oxidation of 10-Methylacridan, a Synthetic Analogue of NADH, and Deprotonation of Its Cation Radical. Convergent Application of Laser Flash Photolysis and Direct and Redox Catalyzed Electrochemistry to the Kinetics of Deprotonation of

ChemInform ◽

10.1002/chin.199125095 ◽

2010 ◽

Vol 22 (25) ◽

pp. no-no

Author(s):

A. ANNE ◽

P. HAPIOT ◽

J. MOIROUX ◽

P. NETA ◽

J.-M. SAVEANT

Keyword(s):

Flash Photolysis ◽

Laser Flash Photolysis ◽

Cation Radical ◽

Laser Flash ◽

Synthetic Analogue ◽

Kinetics Of

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Generation of N,N-Di(4-bromophenyl)nitrenium Ion Under Acidic Conditions: Search for a Nitrenium Dication

10.26434/chemrxiv.11958969.v1 ◽

2020 ◽

Author(s):

Andrea Zeppuhar ◽

Daniel Falvey

Keyword(s):

Flash Photolysis ◽

Laser Flash Photolysis ◽

Cation Radical ◽

Laser Flash ◽

Strong Electron ◽

Nitrenium Ion ◽

Mechanistic Analysis ◽

Separate Pathway ◽

Acidic Conditions ◽

Aqueous Conditions

The behavior of the N,N-di(4-bromophenyl)nitrenium ion under acidic aqueous conditions was examined via laser flash photolysis experiments. A long-lived species forms and can be assigned as the cation radical or the dication. This species is unreactive towards nucleophiles and reactive towards strong electron donors, consistent with a cation radical. Mechanistic analysis indicates its formation is through a separate pathway than that of the nitrenium ion, suggestive of a triplet mechanism.

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Surface photochemistry: Photodegradation study of pyrene adsorbed onto microcrystalline cellulose and silica

International Journal of Photoenergy ◽

10.1155/s1110662x04000261 ◽

2004 ◽

Vol 6 (4) ◽

pp. 205-213 ◽

Cited By ~ 13

Author(s):

A. S. Oliveira ◽

L. F. Vieira Ferreira ◽

J. P. Da Silva ◽

J. C. Moreira

Keyword(s):

Radical Cation ◽

Microcrystalline Cellulose ◽

Ground State ◽

Diffuse Reflectance ◽

Transient Absorption ◽

Flash Photolysis ◽

Laser Flash Photolysis ◽

Cation Radical ◽

Laser Flash ◽

Time Resolved

Ground-state diffuse reflectance, time resolved laser-induced luminescence, diffuse reflectance laser flash-photolysis transient absorption and chromatographic techniques were used to elucidate the photodegradation processes of pyrene adsorbed onto microcrystalline cellulose and silica. Ground-state diffuse reflectance showed that on both substrates low concentrations display absorption of pyrene monomers. At high concentrations spectral changes attributed to aggregate formation were observed. Laser induced fluorescence showed that pyrene onto microcrystalline cellulose mainly presents fluorescence from monomers, while for silica, excimer-like emission was observed from low surface loadings (≥0.5μmolg−1). Transient absorption and photodegradation studies were performed at concentrations where mainly monomers exist. On silica, pyrene presents transient absorption from its radical cation. On microcrystalline cellulose both radical cation, radical anion and pyrene triplet-triplet absorption were detected. Irradiation followed by chromatographic analysis showed that pyrene decomposes on both substrates. For pyrene on microcrystalline cellulose 1-hydroxypyrene was the main identified photoproduct since in the absence of oxygen further oxidation of 1-hydroxypyrene was very slow. For pyrene on silica photodegradation was very efficient. Almost no 1-hydroxypyrene was detected since in the presence of oxygen it is quickly oxidized to other photooxidation products. On both substrates, pyrene radical cation is the intermediate leading to photoproducts and oxygen it is not involved in its formation.

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