ABSTRACT
The reaction of mer-(Ru(H)2(CO)(PPh3)3) (1) with one equivalent of thymine acetic acid (THAcH) unexpectedly produces the macrocyclic dimer k1(O), k2(N,O)-(Ru(CO)(PPh3)2THAc)2 (4) and, concomitantly, the doubly coordinated species k1(O), k2(O,O)-(Ru(CO)(PPh3)2THAc) (5). The reaction promptly forms a complicated mixture of Ru-coordinated mononuclear species. With the aim of shedding some light in this context, two plausible reaction paths were proposed by attributing the isolated or spectroscopically intercepted intermediates on the basis of DFT-calculated energetic considerations. The cleavage of the sterically demanding equatorial phosphine in the mer-species releases enough energy to enable self-aggregation, producing the stable, symmetric 14-membered binuclear macrocycle of 4. The k1-acetate iminol (C=N-OH) unit of the mer-tautomer k1(O)-(Ru(CO)(PPh3)2(THAc)) (2) likely exhibits a stronger nucleophilic aptitude than the prevalent N(H)-C(O) amido species, thus accomplishing extra stabilization through concomitant k2(N,O)-thymine heteroleptic side-chelation. Furthermore, both the ESI-Ms and IR simulation spectra validated the related dimeric arrangement in solution, in agreement with the X-ray determination of the structure. The latter showed tautomerization to the iminol form. The 1H NMR spectra in chlorinated solvents of the kinetic mixture showed the simultaneous presence of 4 and the doubly coordinated 5, in rather similar amounts. THAcH added in excess preferentially reacts with 2 or trans-k2(O,O)-(RuH(CO)(PPh3)2THAc) (3) rather than attacking the starting Complex 1, promptly forming the species of 5. The proposed reaction paths were inferred by spectroscopically monitoring the intermediate species, for which the results were strongly dependent on the of conditions the reaction (stoichiometry, solvent polarity, time, and the concentration of the mixture). The selected mechanism proved to be more reliable, due to the final dimeric product stereochemistry.
ABSTRACT
Despite the media are often described as critical for the success of the well-being agenda, there is wide dissatisfaction with their current level of interest. However, the media coverage of well-being metrics has been unresearched and, even when studies have been conducted, these employed unrobust methodologies, were limited to newspapers and to restricted samples of metrics. This paper fills such gap, providing also for the first time an analysis of radio and TV coverage of well-being metrics. The research was undertaken using Factiva (for newspapers) and TVEyes (for radio and TV) for the years of 2017-2021 and 2018-2021, respectively. The countries analysed are Scotland and Italy, both pioneers in the measurement of well-being. Findings reveal that media coverage of well-being metrics has been extremely low overall and that this was impacted negatively by the COVID-19 pandemic, which instead impacted positively on the reporting of GDP and related queries, showing that the main concern during the pandemic was the impact that this was going to have in terms of output, rather than in terms of well-being. Most composite indices, whose creation is often thought to help obtain greater media coverage, were almost if not even fully ignored by journalists, whereas metrics that lack an overall composite index but that are overseen by independent institutions and have been institutionalised were among the ones that were reported the most.