The low-lying triplet state in p-nitrobenzaldimide

• Published in: International journal of mass spectrometry Vol. 377; pp. 496 - 501
• Main Authors: Rau, Nathan J., Wenthold, Paul G.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.02.2015
• Subjects: Flowing afterglow kinetics; Ion chemistry of imides; Nitric oxide reactions; Triplet anions; Triplet anions; Nitric oxide reactions; Ion chemistry of imides; Flowing afterglow kinetics
• ISSN: 1387-3806; 1873-2798
• DOI: 10.1016/j.ijms.2014.05.008

•We have examined the chemistry of deprotonated imines (imides).•Reactions with CS2 proceed by S/N exchange and hydride transfer.•Reactions with NO show that the p-nitro-substituted ion has a low-lying triplet state.•Electronic structure calculations also predict a triplet state for p-nitro.•p-Nitrobenzaldimide is a rare example of a low-energy triplet anion. Ion–molecule reactions show that p-nitrobenzaldimide, the conjugate-base anion of the benzaldimine, has a low-lying triplet state that is accessible under thermal conditions. Whether it is the ground state or a low-lying excited state cannot be determined, and both possibilities have computational support. Reactivity studies indicate that imide anions with weaker π-donors have singlet ground states, with no evidence for an accessible triplet.