Monoaurated vs. diaurated intermediates: causality or independence?
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F20%3A10414571" target="_blank" >RIV/00216208:11310/20:10414571 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=NL64X-pOv" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=NL64X-pOv</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c9sc05662a" target="_blank" >10.1039/c9sc05662a</a>
Alternative languages
Result language
angličtina
Original language name
Monoaurated vs. diaurated intermediates: causality or independence?
Original language description
Diaurated intermediates of gold-catalysed reactions have been a long-standing subject of debate. Although diaurated complexes were regarded as a drain of active monoaurated intermediates in catalytic cycles, they were also identified as the products of gold-gold cooperation in dual-activation reactions. This study shows investigation of intermediates in water addition to alkynes catalysed by [(IPr)Au(CH3CN)(BF4)]. Electrospray ionisation mass spectrometry (ESI-MS) allowed us to detect both monoaurated and diaurated complexes in this reaction. Infrared photodissociation spectra of the trapped complexes show that the structure of the intermediates corresponds to alpha-gold ketone intermediates protonated or aurated at the oxygen atom. Delayed reactant labelling experiments provided the half life of the intermediates in reaction of 1-phenylpropyne (similar to 7 min) and the kinetic isotope effects for hydrogen introduction to the carbon atom (KIE similar to 4-6) and for the protodeauration (KIE similar to 2). The results suggest that the ESI-MS detected monoaurated and diaurated complexes report on species with a very similar or the same kinetics in solution. Kinetic analysis of the overall reaction showed that the reaction rate is first-order dependent on the concentration of the gold catalyst. Finally, all results are consistent with the reaction mechanism proceeding via monoaurated neutral alpha-gold ketone intermediates only.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
—
Continuities
S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Chemical Science
ISSN
2041-6520
e-ISSN
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Volume of the periodical
11
Issue of the periodical within the volume
4
Country of publishing house
GB - UNITED KINGDOM
Number of pages
9
Pages from-to
980-988
UT code for WoS article
000510929600004
EID of the result in the Scopus database
2-s2.0-85078851618