Efficient unimolecular deprotonation of aniline radical cations

[reaction: see text] Deprotonation of the radical cations of aromatic amines, such as anilines, generally occurs much more slowly than other fragmentation reactions. Here we report a stereoelectronic effect involving twisting of the anilino group out of the plane of the benzene ring that results in a significantly increased rate of reactivity toward deprotonation. Quantitative studies of the rate constants for deprotonation as a function of aniline radical cation pKa (Br?nsted plots) demonstrate that the effect is not simply due to a change in the reaction thermodynamics. By combining this stereoelectronic effect with covalent attachment of carboxylate as a base, aniline radical cations that undergo unimolecular deprotonation with rate constants as high as 10(8) s(-1), even in unfavorable protic media, are described.     

N‐Alkoxyheterocycles As Irreversible Photooxidants

Irreversible photooxidation based on N–O bond fragmentation is demonstrated for N‐methoxyheterocycles in both the singlet and triplet excited state manifolds. The energetic requirements for bond fragmentation are studied in detail. Bond fragmentation in the excited singlet manifold is possible for ππ* singlet states with energies significantly larger than the N–O bond dissociation energy of ca 55 kcal mol^?1. For the nπ* triplet states, N–O bond fragmentation does not occur in the excited state for orbital overlap and energetic reasons. Irreversible photooxidation occurs in the singlet states by bond fragmentation followed by electron transfer. Irreversible photooxidation occurs in the triplet states via bimolecular electron transfer to the donor followed by bond fragmentation. Using these two sensitization schemes, donors can be irreversibly oxidized with oxidation potentials ranging from ca 1.6–2.2 V vs SCE. The corresponding N‐ethylheterocycles are characterized as conventional reversible photooxidants in their triplet states. The utility of these sensitizers is demonstrated by irreversibly generating the guanosine radical cation in buffered aqueous solution.     

Kinetic determinations of accurate relative oxidation potentials of amines with reactive radical cations

Accurate oxidation potentials for organic compounds are critical for the evaluation of thermodynamic and kinetic properties of their radical cations. Except when using a specialized apparatus, electrochemical oxidation of molecules with reactive radical cations is usually an irreversible process, providing peak potentials, E(p), rather than thermodynamically meaningful oxidation potentials, E(ox). In a previous study on amines with radical cations that underwent rapid decarboxylation, we estimated E(ox) by correcting the E(p) from cyclic voltammetry with rate constants for decarboxylation obtained using laser flash photolysis. Here we use redox equilibration experiments to determine accurate relative oxidation potentials for the same amines. We also describe an extension of these experiments to show how relative oxidation potentials can be obtained in the absence of equilibrium, from a complete kinetic analysis of the reversible redox kinetics. The results provide support for the previous cyclic voltammetry/laser flash photolysis method for determining oxidation potentials.     

Data on light-fragment correlations in 40 Ar + 58 Ni at 77 MeV/nucleon

Results of the experimental study of p ⁴ He, d ³ He, dT, pT, p ³ He and, for the first time, nT, n ³ He, n ⁴ He correlations in the region of small relative momenta are presented. The data analysis provides an estimate of the effective source size or emission time.Received: 26 May 2003, Published online: 2 December 2003PACS: 25.70.Pq Multifragment emission and correlations     

Projectile stopping in nucleus-nucleus and hadron-nucleus collisions at 4.2 and 10 GeV/c per nucleon

The collisions ofp,²H,⁴He and C with carbon and tantalum nuclei at 4.2 GeV/c per nucleon as well as the collisionsp-C andp-Ta at 10 GeV/c from 2-m propane bubble chamber have been studied. New results on nuclear stopping have been obtained from the examination of proton rapidity distributions and average rapidity of leading protons for collisions of various degree of centrality: our study points out that a proton projectile is fully stopped in the centralp-Ta collisions at 4.2 GeV/c but only partly stopped at 10 Gev/c. The proton multiplicity in the centralp-Ta collisions at 10 GeV/c can be described by the binomial distribution,P(n), which expresses the probability that the projectile meetsn protons among the nucleons being along the diameter of a target nucleus.