Electrochemical and Chemical Oxidation of Gold(I) Thiolate Phosphine Complexes:  Formation of Gold Clusters and Disulfide

Chen, Jinhua; Jiang, Tong; Wei, Gang; Mohamed, Ahmed A.; Homrighausen, Craig L.; Bauer, Jeanette A. Krause; Bruce, Alice E.; Bruce, Mitchell R. M.

doi:10.1021/ja991986j

Cited by 44 publications

(39 citation statements)

References 16 publications

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“…They react easily with stoichiometric amounts of the appropriate phosphane to yield the corresponding gold(I) phosphane thiolates of formula [Au(SR)(L)] (R = tert-butyl, L = PMe 3 1a, PMe 2 Ph 1b, PMePh 2 1c, PPh 3 1d; R = isobutyl, L = PMe 3 2a, PMe 2 Ph 2b, PMePh 2 2c, PPh 3 2d; R = neopentyl, L = PMe 3 3a, PMe 2 Ph 3b, PMePh 2 3c, PPh 3 3d; R = trityl, L = PMe 3 4a, PMe 2 Ph 4b, PMePh 2 4c, PPh 3 4d). [4e,4h,4i] As far as we know, only [Au(SCMe 3 )(PPh 3 [4c] and 2d by the reaction of [AuCl(PPh 3 )] with the thiol in the presence of a base. [4a] The reactions were carried out in benzene at room temperature, the yields varying from 80 to 95 %.…”

Section: Synthesesmentioning

confidence: 99%

“…[11] In particular the Bruce group has found that gold phosphane thiolates undergo two irreversible oxidation processes, that, in agreement to theoretical studies, were assigned as sulfurand gold-centred, respectively. [3] Chemical complications following oxidation have been elucidated by studying the reaction with ferrocenium tetrafluoroborate. [3] The oxidation process ultimately gives disulfide and a cationic cluster that in the solid state appears to be constituted by a dicationic tetragold system with gold-gold distances that are in the range of typical distances for aurophilic interactions.…”

Section: Oxidation Of Gold Thiolatesmentioning

confidence: 99%

“…[2] In fact some phosphane gold(I) thiolates are the active principles of Auranofin and other antiarthritic products, [3] whose therapeutic activity seems to be correlated to their oxidation products in vivo. In particular Bruce et al, by thoroughly investigating the oxidation of such thiolato-phosphane derivatives, have been able to show that the final products are cationic gold clusters stabilized in the solid state by aurophilic interactions.…”

Section: Introductionmentioning

confidence: 99%

“…In particular Bruce et al, by thoroughly investigating the oxidation of such thiolato-phosphane derivatives, have been able to show that the final products are cationic gold clusters stabilized in the solid state by aurophilic interactions. [3] In spite of many literature reports on the synthesis and properties of gold thiolates, [4] complexes containing simple aliphatic groups have been limited to some scattered scientific reports [4a-4c,4g,4h] and some information deriving from patents. [5] So far attention has mostly been dedicated to the few homoleptic thiolates, which are soluble in organic solvents, [4k] and to the phosphane-thiolato derivatives carrying biologically interesting substrates.…”

Section: Introductionmentioning

confidence: 99%

“…We have also studied triphenylmethanethiol derivatives for comparison purposes. We have prepared homoleptic, neutral derivatives with phosphanes, and the corresponding cationic products prepared according to the Bruce oxidative procedure [3] as a strategy for building gold-gold interactions in the solid state. We report also the structural characterization and a preliminary investigation on the reactivity of these polynuclear cations.…”

Section: Introductionmentioning

confidence: 99%

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Preparation, Structure and Reactivity of Polynuclear Gold(I) Phosphanyl Alkanethiolates

et al. 2007

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The homoleptic gold(I) thiolates of formula [Au(SR)]n (R = CMe3, CH2CMe3, CH2CHMe2, CPh3) have been converted into their phosphane derivatives of general formula [Au(SR)- (L)] (L = PMe3, PMe2Ph, PMePh2, PPh3) and [Au2(SR)2(dppe)] [dppe = 1,2-bis(diphenylphosphanyl)ethane], which have been characterized by elemental analysis, mass spectrometry, 1H and 31P NMR spectroscopy and cyclic voltammetry. Complexes [Au(SCMe3)(PMePh2)] (1c), [Au2(SCMe3)2(dppe)] (1e) and [Au(SCH2CMe3)(PPh3)] (3d) have been characterized in the solid state by X-ray diffraction: no aurophilic interactions have been found. The electrochemical behaviour of these phosphane thiolato derivatives shows two irreversible oxidation processes, the first of which involves 0.5 electrons per Au–SR. Chemical oxidation by [FeCp2]BF4 produces disulfide and cationic gold(I) complexes of formula [Au2(SR)(L)2][BF4] and [Au2(SR)(dppe)][BF4], characterized by elemental analysis, mass spectrometry and 1H and 31P NMR spectroscopy. All the complexes are presumably dimeric in the solid state as shown in the case of [Au4(SCMe3)2-(dppe)2][BF4]2 (5e) and [Au4(SCH2CMe3)2(PMe3)4][BF4]2 (7a), which have been fully characterized by X-ray diffraction. The aurophilic interactions form a structure of four gold atoms with pairs of atoms bonded by bridging thiolato ligands, which are arranged in an almost perfect square in the case of 7a and in an unprecedented zigzag sequence in the case of 5e. Complex 4a reacts with HSCMe3 under basic conditions to give [Au(SCMe3)(PMe3)] and with LiX (X = Me, CH2CMe3) to give a 1:1 mixture of [AuX(PMe3)] and [Au(SCMe3)(PMe3)]

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Section: Synthesesmentioning

confidence: 99%

Section: Oxidation Of Gold Thiolatesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Preparation, Structure and Reactivity of Polynuclear Gold(I) Phosphanyl Alkanethiolates

et al. 2007

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Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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This chapter focuses mainly on closed shell gold(I) atoms which are found to feel attraction among themselves. This attraction is able to modify expected geometries or support one-, two-or three-dimensional arrays and also leads to interesting properties. Closed shell metal cations are expected to repel each other. Nevertheless, an important number of examples containing [d 8 -d 10 -s 2 ] interactions are known. Particularly strong evidence has been accumulated on the attraction between two or more d 10 shells. In the case of gold(I) such attraction between two or more monovalent gold(I) ions in compounds has been observed structurally for a long time. In these situations the gold centers approach each other to a distance of between 2.7 and 3.3 Å. This range includes the distance between gold atoms in gold metal and approaches, or even overlaps with the range of distances found in the few real Au-Au single bonds. Schmidbaur coined the name aurophilic attraction in 1990 and defined it as the unprecedented affinity between gold atoms even with closed-shell electronic configurations and equivalent electrical charges [1]. Since that moment, aurophilicity has become one of the hot topics in gold chemistry, at first with the aim of understanding such interaction, more recently because of the observation that it may play an important role in interesting properties, thus understanding and modulating aurophilic interactions could help to govern these properties, which include the optical behavior. Although different origins are possible for the luminescent emissions of coordination complexes, such as intraligand transitions (ILT), ligand to metal or metal to ligand charge transfer transitions (LMCT, MLCT) and metal centered (MCT) transitions, in many luminescent gold complexes the emissions have been related to the presence of aurophilic interactions.Information about aurophilicity and chemical situations in which it is observed may be found in different works that may be classified as those which analyse closed shell interactions in general [2], those focused on aurophilicity [1,3], and others which analyze the role of these interactions in coordination [4] and organometallic gold Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna

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Characterization Techniques of Organometallic Compounds

Parambath¹,

Mohamed²

2023

Organometallic Compounds

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Electrochemical and Chemical Oxidation of Gold(I) Thiolate Phosphine Complexes: Formation of Gold Clusters and Disulfide

Cited by 44 publications

References 16 publications

Preparation, Structure and Reactivity of Polynuclear Gold(I) Phosphanyl Alkanethiolates

Preparation, Structure and Reactivity of Polynuclear Gold(I) Phosphanyl Alkanethiolates

Gold–Gold Interactions

Characterization Techniques of Organometallic Compounds

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