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Direct Spectroscopic Detection and EPR Investigation of a Ground State Triplet Phenyl Oxenium Ion.
A photoprecursor to the m-dimethylamino phenyloxenium ion is synthesized, which is predicted by both density functional theory and MRMP2 computations to have a triplet ground state electronic configuration, and the triplet oxenium ion reacts via sequential H atom abstractions on the microsecond time domain to ultimately yield the reduced m-Dimethylaminophenol as the only detectable stable photoproduct.
Phenyloxenium ions: more like phenylnitrenium ions than isoelectronic phenylnitrenes?
Values suggest a revision to the current assignments of the ultraviolet photoelectron spectroscopy bands for the phenoxy radical to generate the phenyloxenium ion 1, which is anticipated to be more closely related to closed-shell singlet arylnitrenium ions (Ar-NH(+)) than their isoelectronic arylonitrene ( Ar-N) counterparts.
Direct detection and reactivity of the short-lived phenyloxenium ion.
Photolysis of protonated phenylhydroxylamine was studied using product analysis, trapping experiments, and laser flash photolysis experiments (UV-vis and TR(3) detection) ranging from the femtosecond
Direct spectroscopic observation of closed-shell singlet, open-shell singlet, and triplet p-biphenylyloxenium ion.
These studies provide a rare direct look at a discrete oxenium ion intermediate and the first detection of open-shell singlet and triplet configurations of an oxenium ions, as well as providing an intriguing example of the importance of excited state dynamics in governing the electronic state population of reactive intermediates.
Heteroaryl oxenium ions have diverse and unusual low-energy electronic states.
The electronic state orderings and energies of heteroaryl oxenium ions were computed using high-level CASPT2//CASSCF computations. We find that these ions have a number of diverse, low-energy
Direct observation and reactivity of oxenium ions
Oxenium ions are poorly understood reactive intermediates of the formula R-O. This body of work is an accumulated computational and experimental investigation into understanding the electronic