Gold(iii) compounds containing a chelating, dicarbanionic ligand derived from 4,4′-di-tert-butylbiphenyl

Abstract

An oligomeric gold(III) compound containing dicarbanionic chelating 4,4'-di-tert-butylbiphenyl was prepared via transmetallation using the corresponding organotin(IV) compound. The reactivity of the chloro-bridged oligomer with various species including neutral N-, P-, and C-donor ligands as well as monoanionic S- and Se-ligands was investigated. Some of the products were characterised by X-ray crystallography. The photophysical properties of two derivatives were studied.

Strongly Luminescent Cyclometalated Gold(III) Complexes Supported by Bidentate Ligands Displaying Intermolecular Interactions and Tunable Emission Energy

“…This method was reported by Usón and co‐workers three decades ago . Recently, Mohr's group revisited Usón's method and successfully synthesized a series of [Au III ( t BuC^C)] complexes . This method is a better alternative towards Au III (C^C) complexes than the method using dilithiated biphenyl, which was usually accompanied by the reduction of the gold(III) ion to elemental gold, thereby resulting in a rather low product yield …”

“…In this work, transmetalation using Sn IV dibenzo‐stannole was utilized to prepare the Au III (C^C) precursor complexes, [Au(C^C)Cl] 2 and [Au( t BuC^C)Cl] 2 . Heating a mixture of dibenzo‐stannole and HAuCl 4 ⋅3 H 2 O in acetonitrile at 80 °C afforded precipitates within 0.5 h. After heating overnight, the Au III complexes [Au(C^C)Cl] 2 and [Au( t BuC^C)Cl] 2 were obtained as off‐white solids in 38–50 % yields (see the Supporting Information).…”

Cyclometalated Gold(III) Complexes: Synthesis, Reactivity, and Physicochemical Properties

“…[97] Owing to its poor solubility, 103 could not be characterized by solution NMR spectroscopy but the formation of the corresponding dimer (n = 2) was confirmed by MALDI mass spectrometry.R eactions with donor ligands (e.g., pyridine (Py), 1,3,5-triaza-7-phosphaadmantane (PTA), and xylylisonitrile (XyNC)) or nucleophiles (selenoureas,c arbanions) delivered the corresponding soluble complexes [(C^C)AuCl(L/Nu)] (104 a-f)i ng ood yields. [97] Owing to its poor solubility, 103 could not be characterized by solution NMR spectroscopy but the formation of the corresponding dimer (n = 2) was confirmed by MALDI mass spectrometry.R eactions with donor ligands (e.g., pyridine (Py), 1,3,5-triaza-7-phosphaadmantane (PTA), and xylylisonitrile (XyNC)) or nucleophiles (selenoureas,c arbanions) delivered the corresponding soluble complexes [(C^C)AuCl(L/Nu)] (104 a-f)i ng ood yields.…”

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

“…While these alkyne complexes have so far resisted all attempts at crystallization, structural confirmation of alkyne bonding was unexpectedly obtained from the reaction of 9 15 with AgC≡C t Bu, which gives the thermally stable crystalline products 10 and 11 . The latter, a product of partial reduction, contains a π‐bonded Au(C≡C t Bu) 2 anion, which, probably due to packing effects, displays two types of Au III ‐alkynyl interactions: one symmetrical Au III –alkynyl bond with an elongated C≡C distance of 1.23(3) Å, and one asymmetric alkynyl bridge that shows two very different Au III −C distances (2.29(2) and 2.52(2) Å) and lacks the C≡C bond elongation (Scheme 3).…”