Time‐resolved resonance Raman and density functional theory investigation of the 4‐biphenylnitrene dimerization reaction

Chan, Pik Ying; Ong, Shing Yau; Phillips, David Lee

doi:10.1002/jrs.1230

Cited by 4 publications

(2 citation statements)

References 73 publications

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“…These results combined with the dependence of the 4-biphenylnitrenium ion decay and the 4,4′-azobisbiphenyl growth on the azide concentration strongly suggest that the 4-biphenylnitrenium ion reacts with 4-biphenyl azide to generate the intermediate that subsequently produces the 4,4′-azobisbiphenyl product. The triplet 4-biphenylnitrene was directly observed before in neat acetonitrile to produce 4,4′-azobisbiphenyl . Here, the triplet 4-biphenylnitrene was eliminated because its spectrum does not match that of the intermediate (see Figure 5S in the Supporting Information), which also demonstrates that, at the conditions used here in the TR 3 experiments, the 4-biphenylnitrenium ion will not convert to its conjugate base, the singlet nitrene that can then generate a triplet nitrene by intersystem crossing (ISC).…”

Section: Resultsmentioning

confidence: 81%

“…Samples of 4-biphenyl azide and 4,4′-azobisbiphenyl were synthesized according to the literature methods, , and further details of the synthesis and characterization are given in ref . The 4-biphenyl azide samples were prepared with concentrations ∼1 and ∼2 mM in water:acetonitrile (60:40 by volume) solvent for use in the TR 3 experiments.…”

Section: Experiments and Computation Methodsmentioning

confidence: 99%

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Reaction of the 4-Biphenylnitrenium Ion with 4-Biphenyl Azide to Produce a 4,4′-Azobisbiphenyl Stable Product: A Time-Resolved Resonance Raman and Density Functional Theory Study

Xue

Guan

et al. 2008

J. Phys. Chem. A

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A time-resolved resonance Raman (TR(3)) and density functional theory (DFT) study of the reaction of the 4-biphenylnitrenium ion with 4-biphenyl azide in a mixed aqueous solution is reported. The reaction of the 4-biphenylnitrenium ion with its unphotolyzed precursor 4-biphenyl azide in a mixed aqueous solution generates a 4,4'-azobisbiphenyl stable product via an intermediate species. With the aid of DFT calculations for likely transient species, this intermediate was tentatively assigned to a 4,4'-azobisbiphenyl cation. The DFT calculations predict this reaction can take place via two pathways that compete with one another to produce the trans and cis 4,4'-azobisbiphenyl product. The observation of the 4,4'-azobisbiphenyl cation intermediate demonstrates that the reaction of the arylnitrenium ion with its aryl azide to produce a stable azo product occurs via a stepwise mechanism.

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Section: Resultsmentioning

confidence: 81%

Section: Experiments and Computation Methodsmentioning

confidence: 99%

Reaction of the 4-Biphenylnitrenium Ion with 4-Biphenyl Azide to Produce a 4,4′-Azobisbiphenyl Stable Product: A Time-Resolved Resonance Raman and Density Functional Theory Study

Xue

Guan

et al. 2008

J. Phys. Chem. A

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Time‐Resolved Resonance Raman Spectroscopic Studies of Aryl Nitrenium Ions and their Chemical Reactions

Phillips

2013

Nitrenes and Nitrenium Ions

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Time-Resolved Resonance Raman Observation of the Dimerization of Didehydroazepines in Solution

Xue

Chuang

et al. 2008

J. Phys. Chem. A

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Time-resolved resonance Raman (TR3) studies of the photochemistry of phenyl azide, 3-hyroxyphenyl azide, 3-methoxyphenyl azide and 3-nitrophenyl azide in acetonitrile:water solutions is reported. After photolysis of these four aryl azides in room temperature solutions, only one species was observed in the TR3 spectra for each azide, respectively at the probe wavelengths employed in the TR3 experiments. The species observed after photolysis of 3-nitrophenyl azide was assigned to 3,3'-dinitroazobenzene, an azo compound formed from the dimerization reaction of triplet 3-nitrophenylnitrene. In contrast, the species observed after photolysis of phenyl azide, 3-hydroxyphenyl azide and 3-methoxyphenyl azide were tentatively assigned to intermediates formed from the dimerization of didehydroazepines that are produced from the ring expansion reaction of the respective singlet arylnitrene. To our knowledge, this is the first time-resolved vibrational spectroscopic observation of the dimerization reaction of didehydroazepines in solution. In addition, these are the first resonance Raman spectra reported for dimers formed from didehydroazepines. We briefly discuss the structures, properties and chemical reactivity of the dimer species observed in the TR3 spectra and possible implications for the photochemistry of aryl azides.

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Time‐resolved resonance Raman and density functional theory investigation of the 4‐biphenylnitrene dimerization reaction

Cited by 4 publications

References 73 publications

Reaction of the 4-Biphenylnitrenium Ion with 4-Biphenyl Azide to Produce a 4,4′-Azobisbiphenyl Stable Product: A Time-Resolved Resonance Raman and Density Functional Theory Study

Reaction of the 4-Biphenylnitrenium Ion with 4-Biphenyl Azide to Produce a 4,4′-Azobisbiphenyl Stable Product: A Time-Resolved Resonance Raman and Density Functional Theory Study

Time‐Resolved Resonance Raman Spectroscopic Studies of Aryl Nitrenium Ions and their Chemical Reactions

Time-Resolved Resonance Raman Observation of the Dimerization of Didehydroazepines in Solution

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