RESUMO
Dinuclear bisNHC (bis(N-heterocyclic carbene)) gold(I) complexes 3 a and 4 a of general formula [Au2 Br2 (bisNHC)] were tested as catalysts in the cycloisomerization of N-(prop-2-yn-1-yl)benzamide and in the hydromethoxylation of 3-hexyne in the presence of silver(I) activators bearing different counteranions. The catalytic performance of mononuclear NHC complexes (1 a, 2 a) in the same reactions was also studied. The results highlighted the fundamental role of both NHC ligand and counterion in the catalytic cycles and activation process: dinuclear catalysts exhibit higher initial activity even under milder conditions but suffer in terms of stability with respect to mono NHCs. Furthermore, a new dinuclear bisNHC gold(I) complex 4 b of general formula [Au2 (OTs)2 (bisNHC)] (OTs=p-toluenesulfonate) was successfully synthesized and characterized by means of NMR and ESI-MS analyses.
RESUMO
The ion pairing structure of the possible species present in solution during the gold(III)-catalyzed hydration of alkynes: [(ppy)Au(NHC)Y]X2 and [(ppy)Au(NHC)X]X [ppy = 2-phenylpyridine, NHC = NHCiPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene; NHC = NHCmes = 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene X = Cl-, BF4-, OTf-; Y = H2O and 3-hexyne] are determined. The nuclear overhauser effect nuclear magnetic resonance (NMR) experimental measurements integrated with a theoretical description of the system (full optimization of different ion pairs and calculation of the Coulomb potential surface) indicate that the preferential position of the counterion is tunable through the choice of the ancillary ligands (NHCiPr, NHCmes, ppy, and Y) in [(ppy)Au(NHC)(3-hexyne)]X2 activated complexes that undergo nucleophilic attack. The counterion can approach near NHC, pyridine ring of ppy, and gold atom. From these positions, the anion can act as a template, holding water in the right position for the outer-sphere attack, as observed in gold(I) catalysts.
