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

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
rdfs:seeAlso	http://dx.doi.org/10.1021/ja505945d
Description	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 perfectly correspond with the results from quantum-chemical calculations. 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 perfectly correspond with the results from quantum-chemical calculations. (en)
Title	Role of Gold(I) alpha-Oxo Carbenes in the Oxidation Reactions of Alkynes Catalyzed by Gold(I) Complexes Role of Gold(I) alpha-Oxo Carbenes in the Oxidation Reactions of Alkynes Catalyzed by Gold(I) Complexes (en)
skos:prefLabel	Role of Gold(I) alpha-Oxo Carbenes in the Oxidation Reactions of Alkynes Catalyzed by Gold(I) Complexes Role of Gold(I) alpha-Oxo Carbenes in the Oxidation Reactions of Alkynes Catalyzed by Gold(I) Complexes (en)
skos:notation	RIV/00216208:11310/14:10281757!RIV15-MSM-11310___
http://linked.open...avai/riv/aktivita	I
http://linked.open...avai/riv/aktivity	I
http://linked.open...iv/cisloPeriodika	32
http://linked.open...vai/riv/dodaniDat	2015
http://linked.open...aciTvurceVysledku	Schulz, Jiří Roithová, Jana Jašíková, Lucie Škríba, Anton
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Univerzita Karlova v Praze / Přírodovědecká fakulta
http://linked.open...dnocenehoVysledku	43118
http://linked.open...ai/riv/idVysledku	RIV/00216208:11310/14:10281757
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	bond activation; propargylic alcohols; intermolecular oxidation; terminal alkynes; efficient synthesis; gas-phase; potential-energy surface; ionization mass-spectrometry; photon dissociation spectroscopy; generalized gradient approximation (en)
http://linked.open.../riv/klicoveSlovo	photon dissociation spectroscopy generalized gradient approximation efficient synthesis potential-energy surface terminal alkynes gas-phase ionization mass-spectrometry bond activation intermolecular oxidation propargylic alcohols
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[A037A54C4B69]
http://linked.open...i/riv/nazevZdroje	Journal of the American Chemical Society
http://linked.open...in/vavai/riv/obor	CC
http://linked.open...ichTvurcuVysledku	4 (xsd:int)
http://linked.open...cetTvurcuVysledku	4 (xsd:int)
http://linked.open...UplatneniVysledku	2014
http://linked.open...v/svazekPeriodika	136
http://linked.open...iv/tvurceVysledku	Schulz, Jiří Roithová, Jana Jašíková, Lucie Škríba, Anton
http://linked.open...ain/vavai/riv/wos	000340442700049
issn	0002-7863
number of pages	11 (xsd:int)
http://bibframe.org/vocab/doi	10.1021/ja505945d
http://localhost/t...ganizacniJednotka	11310

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