Stability and reactivity of gold compounds – From fundamental aspects to applications

Đurović, Mirjana; Bugarčić, Živadin D.; Eldik, Rudi van

doi:10.1016/j.ccr.2017.02.015

Cited by 32 publications

(24 citation statements)

References 78 publications

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“…Au(III) easily tends to reduce to Au(I) or Au(0) if electron-rich species are present in the reaction environment [ 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 ]. On the other hand, the ligands that completely stabilize the charge of the metal generate a catalytically non-active complex [ 34 ]. For example, the oxidative addition product, L-AuX 3 , formed from L-AuX (X = halogen) acts as a poorly efficient catalyst and is easily reduced.…”

Section: Introductionmentioning

confidence: 99%

Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences

et al. 2021

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The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl−, BF4−, OTf−, H2O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF4− and OTf− have very similar coordination ability towards [(ppy)Au(IPr)]2+ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]2+ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]2+ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf− and BF4−, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H2O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts.

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Section: Introductionmentioning

confidence: 99%

Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences

et al. 2021

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“…These open‐shell d 9 derivatives, however, are elusive in the condensed phase, and their detection has been possible thanks to unimolecular techniques either in matrices or in the gas phase . Little is known, however, about their chemical behavior . Herein we report on the unexpected formation of the mononuclear [AuCl 3 ] − and [AuBr 3 ] − anions by homolytic splitting of the only Au−C bond in the monoalkyl gold(III) precursors [CF 3 AuX 3 ] − (X=Cl, Br) in the gas phase.…”

Section: Methodsmentioning

confidence: 99%

Gold(II) Trihalide Complexes from Organogold(III) Precursors

Baya

Pérez‐Bitrián

Martínez-Salvador

et al. 2018

Chemistry A European J

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The mononuclear gold(II) halide complexes [AuCl ] and [AuBr ] are formed in the gas phase by collision-induced homolytic splitting of the only Au-C bond in the monoalkylgold(III) precursors [CF AuX ] . The geometries of the whole series of [AuX ] complexes (X=F, Cl, Br, I) have been calculated by DFT methods. It has also been found that the neutral AuX molecules behave as unsaturated species, showing significant affinity for an additional X ligand. Moreover, in the open-shell [AuX ] anions, homolytic splitting of one of the Au-X bonds and formation of the lower-valent [AuX ] anions is favored over non-reducing halide dissociation. They should therefore be prone to disproportionation.

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“…They form bonds with a pronounced degree of covalency due to the high Pauling electronegativity of gold. [4] Interestingly, many gold(I) complexes are not air/moisture sensitive and can be handled as regular organic reagents. Gold(III) complexes are also well known and generally have a square planar geometry with four ligands around the gold(III) cation (dsp 2 hybridization).…”

Section: Introductionmentioning

confidence: 99%

“…The best stability is achieved with soft ligands such as phosphanes, carbenes, thiolates, cyanides. They form bonds with a pronounced degree of covalency due to the high Pauling electronegativity of gold [4] . Interestingly, many gold(I) complexes are not air/moisture sensitive and can be handled as regular organic reagents.…”

Section: Introductionmentioning

confidence: 99%

Chiral Gold(III) Complexes: Synthesis, Structure, and Potential Applications

Jouhannet

Dagorne

Blanc

et al. 2021

Chemistry A European J

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Since the beginning of the 2000's, homogeneous gold catalysis has emerged as a powerful tool to promote the cyclization of unsaturated substrates with excellent regioselectivity allowing the synthesis of elaborated organic scaffolds. An important goal to achieve in gold catalysis is the possibility to induce enantioselective transformations by the assistance of chiral complexes. Unfortunately, the linear geometry of coordination for gold usually encountered in complexes at the + 1 oxidation states renders this goal very challenging. In consequence, the interest toward the synthesis of chiral gold(III) complexes is steadily growing. Indeed, the square planar geometry of the gold(III) cation appears more suitable to promote chiral induction. Beside catalysis, gold(III) complexes have also shown promising potential in the field of pharmacology. Herein, syntheses and applications of well-defined gold(III) complexes reported over the last fifteen years are summarized.

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Stability and reactivity of gold compounds – From fundamental aspects to applications

Cited by 32 publications

References 78 publications

Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences

Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences

Gold(II) Trihalide Complexes from Organogold(III) Precursors

Chiral Gold(III) Complexes: Synthesis, Structure, and Potential Applications

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