A new amine gold(III) complex [Au(C6F5)2(DPA)]ClO4 with the di-(2-picolyl)amine (DPA) ligand has been synthesised. In the solid state the complex has a chiral amine nitrogen because the ligand coordinates to the gold centre through one nitrogen atom from a pyridine and through the NH moiety, whereas in solution it shows a fluxional behaviour with a rapid exchange between the pyridine sites. This complex can be used as an excellent synton to prepare new gold(III) carbene complexes by the reaction with isocyanide CNR. The resulting gold(III) derivatives have unprecedented bidentate C^N acyclic carbene ligands. All the complexes have been spectroscopically and structurally characterized. Taking advantage of the fluxional behaviour of the amine complex, its catalytic properties have been tested in several reactions with the formation of C-C and C-N bonds. The complex showed excellent activity with total conversion, without the presence of a co-catalyst, and with a catalyst loading as low as 0.1%. These complexes also present biological properties, and cytotoxicity studies have been performed in vitro against three tumour human cell lines, Jurkat (T-cell leukaemia), MiaPaca2 (pancreatic carcinoma) and A549 (lung carcinoma). Some of them showed excellent cytotoxic activity compared with the reference cisplatin.
New gold(III) metallacyclic complexes with unprecedented aryl−carbene bidentate ligands have been prepared by the reaction of the cycloaurated gold(III) complex [AuCl 2 (pap-C 1 ,N)] (pap = 2-(2-pyridylamino)phenyl) with isocyanide CNR (R = 2-naphthyl (1), cyclohexyl (2), or 2,6-dimethylphenyl (3)). Complexes have been spectroscopically and structurally characterized, showing in some complexes aurophilic gold(III)•••gold(III) and π−π interactions. In contrast with the starting material these complexes are emissive in the solid state, probably because of the better σ-donor properties of the new bidentate ligands.
A series of gold(I) and gold(III) N-acyclic diamino carbene (ADC) complexes with different ancillary ligands have been synthesized. The chloride carbene derivatives [Au{C(NHR)(NHCH 2 py)}Cl] (R = Cy, R = naphthyl, R = xylyl) have been obtained by reaction of 2-picolylamine with the corresponding [AuCl(CNR)]. The gold(I) thiolate derivatives [Au{C(NHR)(NHCH 2 py)}(Spy)] were prepared by reaction of the chlorido complexes with 2-mercaptopyridine (2-HSpy) in presence of potassium carbonate. The phosphane derivative [Au(pyCH 2 NH 2 )(PPh 3 )](OTf ) was obtained by reaction of freshly prepared [Au(OTf )(PPh 3 )] with 2-picolylamine. The phosphanecarbene complexes [Au{C(NHR)(NHCH 2 py}(PPh 3 )](OTf ) were ob-[a] 4275 Complex 14 crystallizes in the triclinic P1 space group with one molecule by asymmetric unit (Figure 5). The gold(III) atom Eur.4276 displays a distorted square-planar geometry. The angles around the gold(III) atom range from 87.2 to 93.2, the lowest corre-
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