Cyclometallated gold(iii) hydroxides as versatile synthons for Au–N, Au–C complexes and luminescent compounds

Abstract

The gold(III) hydroxide κ(3)-(C^N^C)*Au(OH) reacts with C-H and N-H compounds and arylboronic acids to produce a range of perfluoroaryls, N-heterocyclic and alkynyl compounds in high yields; some of which show unexpectedly strong modulation of their photoluminescence from yellow to blue [(C^N^C)* = 2,6-(C(6)H(3)Bu(t))(2)pyridine].

Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

“…We found recently that C^N^C pincer ligands based on the dianionic 2,6-diphenylpyridine framework are capable of stabilizing a number of novel gold(III) compound types 32,33 , including the first examples of gold(III) hydrides and olefin complexes 34,35 . Given the importance of oxygen ligands in oxidations as well as water cleavage reactions, we decided to explore the reactivity of such gold(III) pincer complexes towards oxygen ligands, including possible Au-O2Au-H interconversions.…”

The interplay between fluorescence and phosphorescence with luminescent gold(i) and gold(iii) complexes bearing heterocyclic arylacetylide ligands

“…13 For the Au( iii ) complexes studied herein, 1b–3b , the lowest-energy triplet excited states are of 3 ππ*(CCR) in nature, with λ max = 630, 592 and 603 nm respectively. These complexes, however, exhibit rather weak phosphorescence, with Φ em values in the range of 0.003–0.04.…”

“…The Au( iii ) complexes 1b–4b were synthesized by copper-catalyzed Sonogashira coupling between terminal alkynes and [Au(C^N^C)Cl] using deoxygenated CH 2 Cl 2 as the solvent, with NEt 3 added to initiate the deprotonation of alkynes. 13 These complexes were purified by chromatography on SiO 2 column using dichloromethane and hexane as eluent. The yields were 51–84%.…”

“…These parameters are similar to those found in related cyclometalated Au( iii ) arylacetylide complexes. 13 The torsional angle between the Au(C^N^C) and arylacetylide planes is approximately 72.6°. This non-planarity gives rise to negligible π–π stacking between molecules as shown in Fig.…”

Synthesis, C–N cleavage and photoluminescence of gold(III) isocyanide complexes

“…(C^N^C)Au(OAc F ) [12], and B(C6F5)3 [24] were prepared using literature methods. 1 H, 13 C{ 1 H} and 19 F spectra were recorded using a Bruker Avance DPX-300 spectrometer.…”