Dua, S.Peppe, S.Bowie, J.2007-02-252007-02-252002Journal of Physical Chemistry A, 2002; 106(43):10470-104761089-56391520-5215http://hdl.handle.net/2440/4622Copyright © 2002 American Chemical SocietyThe two neutral radicals NCCCCO and CCC(O)CN have been made by collision-induced vertical one-electron reduction and oxidation (respectively) of the charged species NCCCCO⁺ and ^- CCC(O)CN. The two charged precursors were prepared by the following reactions: (a) [NC-C≡C-CO-CH<inf>3</inf>]^+. → NCCCO⁺ + CH<inf>3</inf>^. and (b) (CH<inf>3</inf>)<inf>3</inf>Si-C≡C-CO-CN + F^- → n ^-CCC(O)CN + (CH<inf>3</inf>)<inf>3</inf>SiF. Neutral NCCCCO is a stable species, but when energized decomposes by loss of CO to form the radical CCCN [process endothermic by 38.5 kcal mol^-1: calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory]. Neutral CCC(O)CN is 46.8 kcal mol^-1 more positive in energy than the isomer NCCCCO. When energized, CCC(O)CN decomposes by loss of NC to form CCCO (process endothermic by 28.1 kcal mol^-1), but also undergoes a rearrangement process to produce NCCCCO, which is formed with excess energy and may decompose by loss of CO.enJournal article002002092110.1021/jp020524g0001788739000472-s2.0-003720671560069