Gold‐Mediated CI Bond Activation of Iodobenzene

Robinson, Peter S. D.; Khairallah, George N.; Silva, Gabriel da; Lioe, Hadi; O’Hair, Richard A. J.

doi:10.1002/anie.201108502

Cited by 95 publications

(56 citation statements)

References 40 publications

(24 reference statements)

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“…Interestingly, coordination of both phosphine donor arms lowers the activation barrier for the CBr bond cleavage significantly, in contrast to the usual observed reluctance of (bis)phosphine gold(I) complexes to undergo oxidative addition (vide supra) [66].…”

Section: Oxidative Addition Of Aryl Halides To Gold(i)mentioning

confidence: 75%

“…In the course of this controversy concerning the ability of gold(I) complexes to undergo oxidative addition of aryl halides, O'Hair and coworkers [66] investigated the reaction of iodobenzene with gold(I) complexes and small gold clusters by means of mass spectrometry and DFT-computations. While cationic bis(phosphine) gold(I) complexes proved to be inert towards iodobenzene, the monoligated cationic phosphine complexes were shown to undergo C-I activation reactions: iodobenzene and trimethylphosphine or triphenylphosphine gold(I) complexes formed adducts, as indicated by detection of the corresponding cations in the gas phase.…”

Section: Oxidative Addition Of Aryl Halides To Gold(i)mentioning

confidence: 99%

See 1 more Smart Citation

Fundamental Elementary Steps in Gold Chemistry

Joost

2015

Synthesis and Original Reactivity of Copper and Gold Complexes

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Section: Oxidative Addition Of Aryl Halides To Gold(i)mentioning

confidence: 75%

Section: Oxidative Addition Of Aryl Halides To Gold(i)mentioning

confidence: 99%

Fundamental Elementary Steps in Gold Chemistry

Joost

2015

Synthesis and Original Reactivity of Copper and Gold Complexes

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“…[16] Using a bis-ligated cationic gold complex 8, they did not observe any product resulting from oxidative addition by mass spectrometry (1). Calculations confirmed that this reaction was endothermic and had a high activation energy.…”

Section: Methodsmentioning

confidence: 99%

Gold‐Catalyzed Alkynylation: Acetylene‐Transfer instead of Functionalization

Brand¹,

Li²,

Waser³

2013

Israel Journal of Chemistry

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Abstract:In the last fifteen years, gold has raised from the status of an inert noble metal to one of the most often used catalyst in synthetic chemistry. The functionalization of the triple bond of alkynes has been especially successful in this respect. In contrast, gold-catalyzed alkynylation methods have begun to emerge only in 2007. Since then, three different approaches have been successful. Gold nanoparticles allowed catalytic cycles based on oxidative arylation on aryl halides to give a "palladium-free Sonogashira reaction". The use of benziodoxol(on)e hypervalent iodine compounds as oxidative alkynylation reagents had then allowed the C-H functionalization of electron-rich heterocycles under mild conditions and with a very broad functional group tolerance. Finally, the use of iodobenzene acetate or Selectfluor as external oxidant led to the first alkynylation methods based on direct C-H/C-H coupling. In only six years, gold-catalyzed alkynylation methods have raised from nonexistent to useful synthetic protocols for the synthesis of structurally diverse alkynes. When considering that acetylenes are among the most important building blocks for applications in synthetic chemistry, chemical biology and materials science, a tremendous potential for further development of gold-catalyzed alkynylation can be expected for the future.

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“…IMRs within a mass spectrometer can easily rule out such impurities by mass selecting the catalyst of interest. So, in 2012 O'Hair and coworkers studied the gas-phase reactivity of iodobenzene with the mononuclear gold(I) complex [Au(PPh 3 ) 2 ] + and ligated gold clusters [Au 3 L n ] + where L n = Ph 2 P(CH 2 ) n PPh 2 (Scheme 2) [31]. Kinetic analysis of the gas-phase reactions with iodobenzene (Table 1) showed that while the bis-ligated mononuclear gold(I) was inactive with respect to oxidative addition, the ligated gold clusters were active.…”

Section: Oxidative Additionmentioning

confidence: 99%

Mechanistic insights from mass spectrometry: examination of the elementary steps of catalytic reactions in the gas phase

Vikse

McIndoe

2015

Pure and Applied Chemistry

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Real-time mass spectrometric monitoring of speciation in a catalytic reaction while it is occurring provides powerful insights into mechanistic aspects of the reaction, but cannot be expected to elucidate all details. However, mass spectrometers are not limited just to analysis: they can serve as reaction vessels in their own right, and given their powers of separation and activation in the gas phase, they are also capable of generating and isolating reactive intermediates. We can use these capabilities to help fill in our overall understanding of the catalytic cycle by examining the elementary steps that make it up. This article provides examples of how these simple reactions have been examined in the gas phase.

show abstract

Gold‐Mediated CI Bond Activation of Iodobenzene

Cited by 95 publications

References 40 publications

Fundamental Elementary Steps in Gold Chemistry

Fundamental Elementary Steps in Gold Chemistry

Gold‐Catalyzed Alkynylation: Acetylene‐Transfer instead of Functionalization

Mechanistic insights from mass spectrometry: examination of the elementary steps of catalytic reactions in the gas phase

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