Different inorganic and organometallic gold(III) and gold(I) complexes have been tested in the addition of water and methanol to terminal alkynes. Anionic and neutral organometallic gold(III) compounds can efficiently mediate these reactions in neutral media in refluxing methanol. The compounds are added in catalytic amounts (1.6-4.5 mol % with respect to the alkyne). Thus, compounds of the general formula Q[AuRCl(3)], Q[AuR(2)Cl(2)], [AuRCl(2)](2), and [AuR(2)Cl](2) (Q = BzPPh(3)(+), PPN: N(PPh(3))(2)(+) or N(Bu)(4)(+); R = C(6)F(5) or 2,4,6-(CH(3))(3)C(6)H(2)) seem to behave as Lewis acids in nucleophilic additions to triple bonds. Some intermediates could be detected in the stoichiometric reaction between [Au(C(6)F(5))(2)Cl](2) and phenylacetylene that was followed by variable temperature (1)H, (19)F[(1)H], COSY (19)F[(1)H]-(19)F[(1)H], and (2)H[(1)H] NMR experiments. Compound [Au(C(6)F(5))(2)Cl](2) is also able to catalyze the hydration of phenylacetylene at room temperature. A plausible mechanism for the hydration reaction has been proposed.

Two new water‐soluble [IrI2(AcO)(bis‐NHC)] complexes (NHC=N‐heterocyclic carbene) incorporating a sulfonate functionality have been synthesized. The two complexes have been tested in the reduction of CO2 with H2 and iPrOH, and their activity has been compared with similar species without the sulfonate moiety. In both reactions, the complex with the two abnormally bound NHCs shows the best catalytic efficiencies, due to the higher σ‐electron‐donor character of the ligand. Remarkably, the activities obtained for the reduction of CO2 under the transfer hydrogenation conditions are the best reported to date in terms of TON value (max. TON=2700). The two new complexes have also shown very good activity in the selective deuteration of arylamines, a process that is known to proceed through a chelate assisted N‐directed process.

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A series of calix[4]arene-supported Ln(III)(6) clusters have been synthesised under facile bench top conditions. The magnetic and structural properties of these clusters are reported, the latter suggesting that the Ln(III)-calix[4]arene moiety may be used for the construction of other assemblies in a manner akin to that for the Mn(III)-calix[4]arene analogue.

A variety of gold(I) complexes containing the water-soluble phosphine ligands TPPMS, TPPDS, and TPPTS (mono-, di-, and tri-sulfonated triphenylphosphine, respectively) were tested as catalysts for the hydration of phenylacetylene in aqueous media. The gold(I) alkynyl complexes [AuCtCR(TPPTS)] (where R ) t Bu and 3-thiophenyl) give the highest ever reported turnover frequencies (1000 and 1060 h -1 , respectively) for the hydration of phenylacetylene under optimum conditions (0.1 mol % catalyst loading, 10 mol % H 2 SO 4 , 1 h reflux in 5:1 MeOH/H 2 O). The hydration of phenylacetylene can also be carried out using only water and reaction medium, which allows recycling of the gold catalyst without significant drop of activity for at least three cycles. DFT calculations were used to compare relative energies of possible intermediates involved in the catalytic cycle.