Role of Gold(I) alpha-Oxo Carbenes in the Oxidation Reactions of Alkynes Catalyzed by Gold(I) Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F14%3A10281757" target="_blank" >RIV/00216208:11310/14:10281757 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/ja505945d" target="_blank" >http://dx.doi.org/10.1021/ja505945d</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/ja505945d" target="_blank" >10.1021/ja505945d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Role of Gold(I) alpha-Oxo Carbenes in the Oxidation Reactions of Alkynes Catalyzed by Gold(I) Complexes

Popis výsledku v původním jazyce

The gas phase structures of gold(l) complexes formed by intermolecular oxidation of selected terminal (phenylacetylene) and internal alkynes (2-butyne, 1-phenyl-propyne, diphenylacetylene) were investigated using tandem mass spectrometry and ion spectroscopy in conjunction with quantum-chemical calculations. The experiments demonstrated that the primarily formed beta-gold(I) vinyloxypyridinium complexes readily undergo rearrangement, dependent on their substituents, to either gold(I) alpha-oxo carbenenoids (a synthetic surrogate of the a-oxo carbenes) or pyridine adducts of gold(I) enone complexes in the condensed phase and that the existence of naked a-oxo carbenes is highly improbable. Isotopic labeling experiments performed with the reaction mixtures clearly linked the species that exist in solution to the ions transferred to the gas phase. The ions were then fully characterized by CID experiments and IRMPD spectroscopy. The conclusions based on the experimental observations perfect

Název v anglickém jazyce

Role of Gold(I) alpha-Oxo Carbenes in the Oxidation Reactions of Alkynes Catalyzed by Gold(I) Complexes

Popis výsledku anglicky

The gas phase structures of gold(l) complexes formed by intermolecular oxidation of selected terminal (phenylacetylene) and internal alkynes (2-butyne, 1-phenyl-propyne, diphenylacetylene) were investigated using tandem mass spectrometry and ion spectroscopy in conjunction with quantum-chemical calculations. The experiments demonstrated that the primarily formed beta-gold(I) vinyloxypyridinium complexes readily undergo rearrangement, dependent on their substituents, to either gold(I) alpha-oxo carbenenoids (a synthetic surrogate of the a-oxo carbenes) or pyridine adducts of gold(I) enone complexes in the condensed phase and that the existence of naked a-oxo carbenes is highly improbable. Isotopic labeling experiments performed with the reaction mixtures clearly linked the species that exist in solution to the ions transferred to the gas phase. The ions were then fully characterized by CID experiments and IRMPD spectroscopy. The conclusions based on the experimental observations perfect

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

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Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2014

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

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Svazek periodika

136

Číslo periodika v rámci svazku

32

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

11513-11523

Kód UT WoS článku

000340442700049

EID výsledku v databázi Scopus

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