Disulfide Competition for Phosphine Gold(I) Thiolates: Phosphine Oxide Formation vs. Thiolate Disulfide Exchange

Garusinghe, Gamage S. P.; Bessey, S. Max; Aghamoosa, Mostapha; McKinnon, Meaghan; Bruce, Alice E.; Bruce, Mitchell R. M.

doi:10.3390/inorganics3010040

Cited by 7 publications

(6 citation statements)

References 20 publications

(28 reference statements)

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“…The Bruces, Alice Bruce and Mitchell Bruce, from the University of Maine, USA [19], studied the thiol-disulfide exchange reactions which are essential for a number of biochemical transformations. They investigated the mechanism of gold(I) thiolate-disulfide exchange and the conditions which lead to the formation of the competing phosphine oxide.…”

Section: The Present Issuementioning

confidence: 99%

Frontiers in Gold Chemistry

Mohamed

2015

Inorganics

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Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of gold.

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Section: The Present Issuementioning

confidence: 99%

Frontiers in Gold Chemistry

Mohamed

2015

Inorganics

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“…[10][11][12][13][14] We have been investigating metal-mediated thiol-disulfide exchange reactions to understand the mechanism, rate, redox potential and other electronic properties (e.g. [15][16][17] Our goal is to assess the likelihood that Zn 2+ and Au + can influence cellular redox processes involving thiol-disulfide exchange. [15][16][17] Our goal is to assess the likelihood that Zn 2+ and Au + can influence cellular redox processes involving thiol-disulfide exchange.…”

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“…17 In contrast, Ph 3 PvO does not form in acetonitrile and the reaction proceeds cleanly to the product gold(I)-thiolate and mixed disulfide shown in eqn (1) at early stages of the reaction, while at longer reaction times the symmetric disulfide, CH 3 C 6 H 4 SSC 6 H 4 CH 3 , forms. The choice of acetonitrile comes from other preliminary work, which examined the influence of solvent on the reaction of phosphine gold thiolates and disulfides.…”

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The influence of gold(i) on the mechanism of thiolate, disulfide exchange

et al. 2016

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The mechanism of gold(i)-thiolate, disulfide exchange was investigated by using initial-rate kinetic studies, 2D ((1)H-(1)H) ROESY NMR spectroscopy, and electrochemical/chemical techniques. The rate law for exchange is overall second order, first order in gold(i)-thiolate and disulfide. 2D NMR experiments show evidence of association between gold(i)-thiolate and disulfide. Electrochemical/chemical investigations do not show evidence of free thiolate and are consistent with a mechanism involving formation of a [Au-S, S-S], four-centered metallacycle intermediate during gold(i)-thiolate, disulfide exchange.

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“…Some examples include: playing an essential role as a ligand for transition metal catalysts, 9,10 an oxidant for the oxidation of thiols or alcohols, 11,12 and a participant in the oxidation of gold phosphine complexes. 13 We have employed DMSO as a solvent in our kinetic studies of the inuence of solvent dielectric on metal thiolate-disulde exchange reactions. [14][15][16] Our interest lies in comparing metalmediated thiolate-disulde exchange to metal-free thiol-disulde exchange, the latter of which proceeds at a slower rate in high dielectric solvents, such as water or DMSO, than in low dielectric solvents such as THF or CH 2 Cl 2 .…”

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Identification of dimethyl sulfide in dimethyl sulfoxide and implications for metal-thiolate disulfide exchange reactions

et al. 2015

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The concentration of dimethyl sulfide (DMS) in seven different samples of research grade dimethyl sulfoxide (DMSO), including one deuterated sample, was measured by GC-MS. The average concentration of DMS is 0.48 AE 0.14 mM (range: 0.44-0.55 mM) and ca. 0.35 mM in DMSO-d 6 . The presence of DMS in DMSO is potentially problematic for compounds that are susceptible to reaction with DMS and are present at mM-mM concentrations. Standard methods of purification of DMSO were unsuccessful in removing all traces of DMS.Dimethyl sulfoxide (DMSO) is an aprotic, polar solvent that is widely used in chemistry and biology. It dissolves hydrophobic and hydrophilic solutes, 1-4 is used as a cryoprotectant for biological samples, 5 and is a component in drug delivery. 6 Researchers have taken advantage of the miscibility of DMSO with water, organic solvents, and ionic liquids (IL) to solubilize polymers and enhance reaction chemistry. For example, recent reports describe the benecial effects of a DMSO : IL co-solvent as a green solvent for hydrolysis of cellulose; 7 and a DMSO : water co-solvent to promote thiol-disulde dynamic combinatorial chemistry. 8 DMSO can also participate in reactions. Some examples include: playing an essential role as a ligand for transition metal catalysts, 9,10 an oxidant for the oxidation of thiols or alcohols, 11,12 and a participant in the oxidation of gold phosphine complexes. 13 We have employed DMSO as a solvent in our kinetic studies of the inuence of solvent dielectric on metal thiolate-disulde exchange reactions. 14-16 Our interest lies in comparing metalmediated thiolate-disulde exchange to metal-free thioldisulde exchange, the latter of which proceeds at a slower rate in high dielectric solvents, such as water or DMSO, than in low dielectric solvents such as THF or CH 2 Cl 2 . 17 Since the metal thiolate complexes and disuldes employed in our kinetic studies are not water-soluble, DMSO was selected as a solvent with a high dielectric constant (3 ¼ 46.45) 1 for these studies. During the course of kinetic investigations, we observed that addition of bis(4-nitrophenyl)disulde to DMSO, in the absence of any metal thiolate, formed a pale red solution with an absorbance near 500 nm. Bis(4-nitrophenyl)disulde is isolated as a pale yellow solid aer recrystallization from boiling nbutanol. When the disulde is dissolved in solvents such as CH 2 Cl 2 , CH 3 CN, acetone, or THF, the solution does not turn red (i.e. there is no absorbance at 500 nm). We suspected that the species responsible for the color in solutions of DMSO was 4-nitrophenylthiolate because addition of base (NEt 3 ) to a DMSO solution of 4-nitrophenylthiol produced a similar red solution with l max ¼ 502 nm. 18 Over the course of time, we observed that when bis(4-nitrophenyl)disulde is dissolved in a variety of DMSO solvents obtained from different commercial suppliers, a similar red color was produced. Thus, we hypothesized that an impurity in DMSO reacts with the disulde to form 4-nitrophenylthiolate. DMSO is an odorle...

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Disulfide Competition for Phosphine Gold(I) Thiolates: Phosphine Oxide Formation vs. Thiolate Disulfide Exchange

Cited by 7 publications

References 20 publications

Frontiers in Gold Chemistry

Frontiers in Gold Chemistry

The influence of gold(i) on the mechanism of thiolate, disulfide exchange

Identification of dimethyl sulfide in dimethyl sulfoxide and implications for metal-thiolate disulfide exchange reactions

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