Keywords: Gold chemistry, Gold catalysis, NMR, DFT, Organometallic catalysis, Relativistic effects ERC research sectors:
BackgroundOwing to the millenary reputation of elementary gold as the archetypal "noble", chemically inert metal, chemists were late in discovering its rich chemistry and, in particular, in observing that compounds of the type [L-Au(I)-S]X (where L is a neutral ligand, eg a phosphine or an eterocyclic carbene, and X- a weakly coordinating anion) can catalytically activate a wide range of unsaturated substrates (S) usually unreactive towards nucleophilic addition: Since the late 80's, scientific exploration in this field has been explosively growing. Appealing features of Au(I)-based catalysis are:
ObjectiveAs is typical of the early life of a technology, the major aim of current research has been that of achieving know-how on an essentially empirical basis. Attempts to understand the theoretical and mechanistic foundations of this chemistry, in order for know-why to evolve alongside know-how, are scarce, not least because of the general difficulty of adequately describing heavy-metal compounds, profoundly influenced both by electron correlation and, in particular, by relativistic effects. The latter have only recently become amenable to realistic computational modeling. As a result, a reliable, undisputed, interpretive framework, in which to describe a metal-substrate bonding, is still missing.The objective of the AuCat project is to give a significant contribution towards the understanding of the basic mechanisms, so far largely unknown, which govern the chemistry of "coinage metal" catalysts, and in particular those of Au(I) in the homogeneous phase. Research linesUndertaking such task with acceptable odds of success requires complementary state-of-the-art skills to be simultaneously and synergically employed along the following research lines:
Research lines 1., 2. and 3. are carried out by three cooperating Research units (RUs) based in Perugia, Napoli and Udine. |