Ruthenium-triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox-neutral C-C bond cleavage of the β-O-4 lignin linkage of 1,3-dilignol model compounds. A mechanistic pathway involving a dehydrogenation-initiated retro-aldol reaction for the C-C bond cleavage was proposed in line with experimental data and DFT calculations.
Intermolecular Coulombic decay (ICD) is a very fast and efficient relaxation pathway of ionized and excited molecules in environment. The ICD and related phenomena initiated by inner-valence ionization are explored for H(2)O···HCHO, H(2)O···H(2)CNH, H(2)O···NH(3), NH(3)···H(2)O, H(2)O···H(2)S, H(2)S···H(2)O, and H(2)O···H(2)O (p-donor···p-acceptor). This set of small hydrogen-bonded systems contains seven types of hydrogen bonding, which are typical for biochemistry, and thus its investigation provides insight into the processes that can take place in living tissues. In particular, an estimate of the ICD in biosystems interacting with water (their usual medium) is made. This decay mode is expected to be a source of low-energy electrons proven to be of extreme genotoxic nature. For the purpose of our study, we have used high-precision ab initio methods in optimizing the geometries and computing the single- and double-ionization spectra of formaldehyde-, formaldimine-, ammonia-, hydrogen sulfide-, and water-water complexes. The energy range of the emitted ICD electrons, as well as the kinetic energy of the dissociating ions produced by ICD, is also reported.
We report the first observation of electron-transfer-mediated decay (ETMD) and interatomic Coulombic decay (ICD) from the triply charged states with an inner-valence vacancy, using the Ar dimer as an example. These ETMD and ICD processes, which lead to fragmentation of Ar(3+)-Ar into Ar(2+)-Ar(2+) and Ar(3+)-Ar+, respectively, are unambiguously identified by electron-ion-ion coincidence spectroscopy in which the kinetic energy of the ETMD or ICD electron and the kinetic energy release between the two fragment ions are measured in coincidence.
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