KOPS - Das Institutionelle Repositorium der Universität Konstanz

Formation and Reactions of Tetracarbonyl Intermediates of the Fischer Carbene Complex (CO)5W=C(OMe)Ph : A Laser Flash Photolysis Study Using Time-Resolved Infrared and UV/Vis Spectroscopy

Formation and Reactions of Tetracarbonyl Intermediates of the Fischer Carbene Complex (CO)5W=C(OMe)Ph : A Laser Flash Photolysis Study Using Time-Resolved Infrared and UV/Vis Spectroscopy

Zitieren

Dateien zu dieser Ressource

Prüfsumme: MD5:2a1d2df3d5a4cfc9726a1ad33e4e961c

GUT, Hans-Peter, Nicolas WELTE, Uwe LINK, Helmut FISCHER, Ulrich STEINER, 2000. Formation and Reactions of Tetracarbonyl Intermediates of the Fischer Carbene Complex (CO)5W=C(OMe)Ph : A Laser Flash Photolysis Study Using Time-Resolved Infrared and UV/Vis Spectroscopy. In: Organometallics. 19(12), pp. 2354-2364. ISSN 0276-7333. eISSN 1520-6041

@article{Gut2000Forma-9582, title={Formation and Reactions of Tetracarbonyl Intermediates of the Fischer Carbene Complex (CO)5W=C(OMe)Ph : A Laser Flash Photolysis Study Using Time-Resolved Infrared and UV/Vis Spectroscopy}, year={2000}, number={12}, volume={19}, issn={0276-7333}, journal={Organometallics}, pages={2354--2364}, author={Gut, Hans-Peter and Welte, Nicolas and Link, Uwe and Fischer, Helmut and Steiner, Ulrich} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/9582"> <dc:contributor>Steiner, Ulrich</dc:contributor> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T18:12:55Z</dc:date> <dcterms:issued>2000</dcterms:issued> <dc:creator>Link, Uwe</dc:creator> <dc:creator>Welte, Nicolas</dc:creator> <dc:rights>deposit-license</dc:rights> <dc:contributor>Fischer, Helmut</dc:contributor> <dc:creator>Gut, Hans-Peter</dc:creator> <dc:contributor>Welte, Nicolas</dc:contributor> <dcterms:abstract xml:lang="eng">The results of nanosecond laser flash photolysis (XeCl excimer irradiation at 308 nm) of the Fischer carbene complex [(CO)5W=C(OMe)Ph] (CZ) in di-n-butyl ether and n-hexane are reported. Spectrokinetical detection of the intermediates was based on transient absorptions simulaneously recorded in the UV/vis and the IR spectral regions. The primary photoproducts are the unstable isomer CE produced with a quantum yield of about 30% and a tetracarbonyl complex I-S, probably of structure [(CO)4(S)W=C(OMe)Ph], where S is a solvent molecule. The quantum yield of CO photoelimination was estimated as 1.7%. The CE isomer was found to return to the stable CZ isomer within a few microseconds, confirming previous results of McGarvey and co-workers. The tetracarbonyl species reacts with cosolutes present in the solution such as N2, H2O, acetonitrile, and methyl trans-crotonate to form secondary complexes of cis-tetracarbonyl complex structure [(CO)4(L)W=C(OMe)Ph] (I-L). The tetracarbonyl complexes react readily with CO. For I-N2 in n-hexane the rate constant is 3.5 × 108 M-1 s-1. The rate constants of the corresponding reactions with acetonitrile (MeCN) and the olefin are larger by a factor of 2. In the presence of CO the complexes I-MeCN and I-olefin revert to CZ in a dissociative reaction mechanism. The rate constants for the elimination of MeCN or olefin are 5 and 105 s-1, respectively. The I-olefin complex irreversibly decomposes with a rate constant of 8 × 103 s-1.</dcterms:abstract> <dc:format>application/pdf</dc:format> <dc:creator>Fischer, Helmut</dc:creator> <dc:language>eng</dc:language> <dcterms:rights rdf:resource="https://creativecommons.org/licenses/by-nc-nd/2.0/legalcode"/> <dc:creator>Steiner, Ulrich</dc:creator> <dcterms:title>Formation and Reactions of Tetracarbonyl Intermediates of the Fischer Carbene Complex (CO)5W=C(OMe)Ph : A Laser Flash Photolysis Study Using Time-Resolved Infrared and UV/Vis Spectroscopy</dcterms:title> <dc:contributor>Link, Uwe</dc:contributor> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/9582"/> <dcterms:bibliographicCitation>First publ. in: Organometallics ; 19 (2000), 12. - S. 2354-2364</dcterms:bibliographicCitation> <dc:contributor>Gut, Hans-Peter</dc:contributor> </rdf:Description> </rdf:RDF>

Dateiabrufe seit 01.10.2014 (Informationen über die Zugriffsstatistik)

Formation_and_Reactions_of_Tetracarbonyl_Intermediates_of_the_Fischer_Carbene_Complex.pdf 283

Das Dokument erscheint in:

deposit-license Solange nicht anders angezeigt, wird die Lizenz wie folgt beschrieben: deposit-license

KOPS Suche


Stöbern

Mein Benutzerkonto