Internal energies and energy distributions were studied using the 'survival yield' method developed previously. In addition to conventional benzylpyridinium salts, protonated esters (fragmenting by rearrangement) and protonated leucine enkephalin were also used, extending the validity of the technique. Fragmentation processes were studied in the cone voltage region and modeled by the RRKM-based MassKinetics program. The results show that the shapes of the energy distributions are similar to thermal distributions. The mean internal energies are very similar for all compound classes studied, and show a linear increase with collision energy in the 10-50 eV region.

The well-established oxidative addition -reductive elimination pathway is the most followed one in transition metal catalyzed cross coupling reactions. While readily occurring with a series of transition metals, it does not take place with gold(I) complexes which have shown some reluctance to undergo oxidative addition unless special sets of ligands on gold(I), reagents or reaction conditions are used. A new possibility to overcome this hurdle has been devised. Upon visible light irradiation, an iridium photocatalyst triggers via triplet sensitization the oxidative addition of an alkynyliodide onto a vinylgold(I) intermediate to deliver Csp 2 -Csp coupling products after reductive elimination. Mechanistic and modeling studies support that an energy transfer takes place and not a redox pathway. This novel mode of activation in gold homogenous catalysis was applied in several dual catalytic processes. Alkynylbenzofuran derivatives were obtained from o-alkynylphenols and iodoalkynes in the presence of catalytic gold(I) and iridium(III) complexes under blue LED irradiation.Over the last two decades, homogeneous gold catalysis has been extensively used to efficiently and selectively promote a variety of cyclization processes. [1][2][3] The typical casting involves bifunctional substrates bearing an unsaturation prompt to electrophilic activation and a judiciously positioned internal nucleophile. A protodemetalation of the organogold intermediates to afford hydrofunctionalized products generally terminates the catalytic cycles. 4 Pursuing the step economy principle and also aiming at higher level of molecular complexity, some in situ post-functionalization reactions of the organogold 5 intermediate have been devised such as electrophilic halogenation or cross-coupling reactions. Although palladium catalyzed cross coupling from an organogold(I) intermediate has been