The role of peroxyl radicals in polyester degradation--a mass spectrometric product and kinetic study using the distonic radical ion approach.

Mass spectrometric techniques were used to obtain detailed insight into the reactions of peroxyl radicals with model systems of (damaged) polyesters. Using a distonic radical ion approach, it was shown that N-methylpyridinium peroxyl radical cations, Pyr(+)OO˙, do not react with non-activated C-H bonds typically present in polyesters that resist degradation. Structural damage in the polymer, for example small amounts of alkene moieties formed during the manufacturing process, is required to enable reaction with Pyr(+)OO˙, which proceeds with high preference through addition to the π system rather than via allylic hydrogen atom abstraction (kadd/kHAT > 20 for internal alkenes). This is due to the very fast and strongly exothermic subsequent fragmentation of the peroxyl-alkene radical adduct to epoxides and highly reactive Pyr(+)O˙, which both could promote further degradation of the polymer through non-radical and radical pathways. This work provides essential experimental support that the basic autoxidation mechanism is a too simplistic model to rationalize radical mediated degradation of polymers under ambient conditions.

Gas-phase reactions of aryl radicals with 2-butyne: experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation.

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH(3)C≡CCH(3)) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH(3) loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP+2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C(4) side-chain, followed by cyclization and/or low-energy H atom ß-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph˙)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH(3) loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid molecular weight growth reactions to yield polycyclic aromatic nitrogen hydrocarbons (PANHs).

Structural and photochemical properties of organosilver reactive intermediates MeAg2(+) and PhAg2(+).

Although there is growing interest in silver promoted carbon-carbon bond formation, a key challenge in developing robust and reliable organosilver reagents is that thermal and photochemical decomposition reactions can compete with the desired coupling reaction. These undesirable reactions have been poorly understood due to complications arising from factors such as solvent effects and aggregation. Here the unimolecular decomposition reactions of organosilver cations, RAg(2)(+), where R = methyl (Me) and phenyl (Ph), are examined in the gas phase using a combination of mass spectrometry based experiments and theoretical calculations to explore differences between thermal and photochemical decompositions. Under collision-induced dissociation conditions, which mimic thermal decomposition, both PhAg(2)(+) and MeAg(2)(+) fragment via formation of Ag(+). The new ionic products, RAg(+•) and Ag(2)(+•), which arise via bond homolysis, are observed when RAg(2)(+) is subject to photolysis using a UV-vis tunable laser OPO. Furthermore, comparisons between the theoretical and experimental UV-vis spectra allow us to unambiguously determine the most stable structures of PhAg(2)(+) and MeAg(2)(+) and to identify the central role of the silver part in the optical absorption of these species. The new photoproducts result from fragmentation in electronic excited states. In particular, potential energy surface calculations together with the fragment charges highlight the role of triplet states in these new fragmentation schemes.

Synthesis and Spectroscopic Characterization of Diphenylargentate, [(C6H5)2Ag](.).

We present the structural and optical properties of the isolated diphenylargentate anion, which has been synthesized by multistage mass spectrometry in a quadrupole ion trap. The experimental photodetachment spectrum has been obtained by action spectroscopy. Comparison with quantum chemical calculations of the electronic absorption spectrum allows for a precise characterization of the spectroscopic features, showing that in the low-energy regime, the optical properties of diphenylargentate bear a significant resemblance to those of atomic silver.