Scheme3.ReactionofP hI(OAc) 2 with two TMS-OTf stoppingatP hI(OTf)(OAc). Scheme4.ReactionofP hI(OAc) 2 with 2-oxazolines in the presence of two TMS-OTf,which was proposedtop roceed via PhI(OTf) 2 as an intermediate.
Stable difluorogold(iii) complexes can be easily synthesized either via oxidation of N-ligated cationic Au(i) precursors using XeF2 or from tricationic Au(iii) precursors by displacement of the N-ligands using fluoride from economical KF. X-ray crystallographic studies of the bisimidazole ligated derivative shows the shortest Au-F bond known in a gold complex.
A novel synthetic approach for the synthesis of gold(iii) acetato, alkoxolato and alkynyl complexes was developed via the reactivity of gold(iii) trications containing the N,N-chelating ligand 2,2'-bipyridine and N,N,N-chelating ligand terpyridine through direct reactions with the protic precursors. This protocol avoids the gold(iii) chloride bond activation pathway commonly employed to access these functionalities. For example exposure of [LAu(iii)L']OTf (L = N,N,N-terpyridine, L' = 4-DMAP) to RH (R = OCH, OAc, Ph-[triple bond, length as m-dash]) results in the facile formation of the corresponding functionalised gold(iii) complexes [LAu(iii)R]OTf.
We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr)][OTf] (Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either -IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr)][OTf] gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner.
We report the synthesis and characterization of cationic Au(III) complexes supported by nitrogen-based ligands. The synthesis is achieved by reacting Au(I) complexes [Au(N-Me-imidazole)2] + and [Au(pyridine)(NHC)] + with iodine(III) reagents yielding a series of cationic gold(III) complexes. In contrast, reactions of phosphine ligated gold(I) complexes with iodine(III) reagents resulted in the oxidation of the phosphine ligand.
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