American Chemical Society
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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

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journal contribution
posted on 2008-11-20, 00:00 authored by Jiadan Xue, Yong Du, Xiangguo Guan, Zhen Guo, David Lee Phillips
A time-resolved resonance Raman (TR3) 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.