TY - DATA T1 - 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 PY - 2008/11/20 AU - Jiadan Xue AU - Yong Du AU - Xiangguo Guan AU - Zhen Guo AU - David Lee Phillips UR - https://acs.figshare.com/articles/journal_contribution/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/2898529 DO - 10.1021/jp805353q.s001 L4 - https://ndownloader.figshare.com/files/4596670 KW - biphenyl KW - biphenylnitrenium KW - solution KW - cation KW - species KW - Raman KW - azide KW - azobisbiphenyl KW - TR KW - DFT calculations N2 - 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. ER -