Gold–Gold Cooperation in the Addition of Methanol to Alkynes

Roithová, Jana; Janková, Štěpánka; Jašíková, Lucie; Váňa, Jiří; Hybelbauerová, Simona

doi:10.1002/anie.201204003

Cited by 80 publications

(53 citation statements)

References 53 publications

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“…13,[26][27][28][29][30][31][32][33] Complexes in the frames can be detected by ESI-MS. 13 The symbol (LAu + )* is used for an active form of the catalyst.…”

Section: Methodsmentioning

confidence: 99%

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Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

et al. 2015

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A new method to investigate the reaction kinetics of intermediates in solution by electrospray ionization mass spectrometry is presented. The method, referred to as delayed reactant labeling, allows investigation of a reaction mixture containing isotopically labeled and unlabeled reactants with different reaction times. It is shown that we can extract rate constants for the degradation of reaction intermediates and investigate the effects of various reaction conditions on their half-life. This method directly addresses the problem of the relevance of detected gaseous ions toward the investigated reaction solution. It is demonstrated for geminally diaurated intermediates formed in the gold mediated addition of methanol to alkynes. Delayed reactant labeling allows us to directly link the kinetics of the diaurated intermediates with the overall reaction kinetics determined by NMR spectroscopy. It is shown that the kinetics of protodeauration of these intermediates mirrors the kinetics of the addition of methanol demonstrating they are directly involved in the catalytic cycle. Formation as well as decomposition of diaurated intermediates can be drastically slowed down by employing bulky ancillary ligands at the gold catalyst; the catalytic cycle then proceeds via monoaurated intermediates. The reaction is investigated for 1-phenylpropyne (Ph-CC-CH3) using [AuCl(PPh3)]/AgSbF6 and [AuCl(IPr)]/AgSbF6 as model catalysts. Delayed reactant labeling is achieved by using a combination of CH3OH and CD3OH or Ph-CC-CH3 and Ph-CC-CD3.

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“…13,[26][27][28][29][30][31][32][33] Complexes in the frames can be detected by ESI-MS. 13 The symbol (LAu + )* is used for an active form of the catalyst.…”

Section: Methodsmentioning

confidence: 99%

“…This regioselectivity is thermodynamically favored (see also results of DFT calculations). 13 Using the [AuCl(PPh 3 )] catalysts, the C (1) addition is slightly preferred. We have also tested the effect of acid addition.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

et al. 2015

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“…In the ESI-MS timeresolved study by Jiang, Xie,a nd co-workers,t he gold(I) precursor and the gold NC intermediate species were identified and monitored over time ( Figure 13). This time course of gold NC formation revealed the existence of an initial kinetically controlled reduction-growth mechanism and subsequent thermodynamically guided intercluster conversion into [Au 25 (SR) 18 ] À . [60] In the growing research area of BÀN( boron-nitrogen) materials,s uch as those isoelectronic with polyolefins and white graphene,W eller, Macgregor and co-workers recently reported amechanistic investigation of the iridium-mediated dehydropolymerization of amine-boranes.…”

Section: Monitoring Polymer Growthmentioning

confidence: 96%

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

2016

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Just as periscopes allow a submarine to visually search for objects above the surface of the sea, in a reversed periscope fashion electrospray mass spectrometry (ESI-MS) can analyze the compounds at the gas phase/liquid phase interface for chemical entities which may exist in solution. The challenge is the identification and structural characterization of key elusive reaction intermediates in chemical transformations, intermediates which are able to explain how chemical processes occur. This Minireview summarizes recent selected publications on the use of ESI-MS techniques for studying solution intermediates of homogeneous chemical reactions.

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“…[10] With the ability to isolate specific gold cations, MS provides the opportunity to evaluate the reactivity of certain gold-containing cations, which will greatly help the elucidation of the reaction mechanism. [11] The reaction we selected for this investigation was the hydration of propargyl acetate alkyne 1 owing to the existence of both a terminal alkyne (formation of s,p-diaurated gold acetylides) and the intramolecular nucleoside (acetate).…”

Section: Introductionmentioning

confidence: 99%

Direct Evidence for the Origin of Bis‐Gold Intermediates: Probing Gold Catalysis with Mass Spectrometry

Lü

Zhao

et al. 2018

Chemistry A European J

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Gold-catalyzed alkyne hydration was studied by using in situ reacting mass spectrometry (MS) technology. By monitoring the reaction process in solution under different conditions (regular and very diluted catalyst concentrations, different pH values) and examining the reaction occurrence in the early reaction stage (1–2 ms after mixing) with MS, we collected a series of experimental evidence to support that the bis-gold complex is a potential key reaction intermediate. Furthermore, both experimental and computational studies confirmed that the σ,π-bis-gold complexes are not active intermediates toward nucleophilic addition. Instead, formation of geminally diaurated complex C is crucial for this catalytic process.

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Gold–Gold Cooperation in the Addition of Methanol to Alkynes

Cited by 80 publications

References 53 publications

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

Direct Evidence for the Origin of Bis‐Gold Intermediates: Probing Gold Catalysis with Mass Spectrometry

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