Resource Management Agency

Gold(iii) complexes are garnering increasing interest for opto-electronic, therapeutic and catalytic applications. But so far, very little is known about the factors controlling their reactivity and the very influence of the ancillary ligand. This article reports the first comprehensive study on this topic. The reactivity of a cationic (N,C) gold(iii) complex, namely 1A, towards ethylene has been thoroughly studied and compared with that of the related (P,C) complex 1C. A cationic gold(iii) complex 5A resulting from double insertion of ethylene was selectively obtained. Complex 5A was found to be remarkably stable. It was trapped with chloride and fully characterized. In marked contrast to that observed with 1C, no β-H elimination or linear-to-branched rearrangement of the alkyl chain occurred with 1A. The energy profile for the reactions of 1A with ethylene has been comprehensively investigated computationally, and the influence of the ancillary ligand has been precisely delineated. Because nitrogen is a weaker donor than carbon (and phosphorus), the (N,C) ligand is very electronically dissymmetric, much more than the (P,C) ligand. This makes the two reactive sites at gold quite different, which noticeably influences the competition between migratory insertion and β-H elimination, and actually changes the outcome of the olefin insertion at gold. This study provides valuable insight into the influence of ancillary ligands on gold(iii) reactivity, something critical to further develop Au(iii) and Au(i)/Au(iii) catalysis.

Au(iii)-aryl species have been unequivocally identified as reactive intermediates in oxidant-free C-O and C-N cross coupling catalysis. The crystal structures of cyclometalated neutral and cationic Au(iii) species are described and their key role in 2 electron-redox Au(i)/Au(iii) catalysis in C-O and C-N cross couplings is shown. Nucleophiles compatible with Au-catalyzed cross couplings include aromatic and aliphatic alcohols and amines, as well as water and amides.

Standards provide harmonization insofar as they are agreed means of doing something. They define requirements for offering a service, specifications for data exchange, compatibility conditions, security measures, or process qualifications. Standards deal, then, with numerous activities where organizations and customers are involved. The translation and localization industry is also guided by standards, set by experts representing sellers, buyers, customers, associations, users or regulators. This special issue of Tradumàtica, co-edited by Willem Stoeller and Celia Rico, gathers contributions from some of these experts, addressing standards in translation and localization both from an academic perspective and the industry point of view.