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http://dx.doi.org/10.18419/opus-7959
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DC Element | Wert | Sprache |
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dc.contributor.author | Gudat, Dietrich | de |
dc.contributor.author | Schiffner, Hans M. | de |
dc.contributor.author | Nieger, Martin | de |
dc.contributor.author | Stalke, Dietmar | de |
dc.contributor.author | Blake, Alexander J. | de |
dc.contributor.author | Grondey, Hiltrud | de |
dc.contributor.author | Niecke, Edgar | de |
dc.date.accessioned | 2012-05-24 | de |
dc.date.accessioned | 2016-03-31T11:44:45Z | - |
dc.date.available | 2012-05-24 | de |
dc.date.available | 2016-03-31T11:44:45Z | - |
dc.date.issued | 1992 | de |
dc.identifier.other | 37036645X | de |
dc.identifier.uri | http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-74338 | de |
dc.identifier.uri | http://elib.uni-stuttgart.de/handle/11682/7976 | - |
dc.identifier.uri | http://dx.doi.org/10.18419/opus-7959 | - |
dc.description.abstract | Novel iminophosphanes of the type (Me5C5)P=NR [R = C6H2tBu3 (5a), Si-i-Pr3 (5b), SiMe3 (5c)] are prepared via either thermolytic or base-promoted elimination reactions and characterized by analytical and spectroscopic methods. The x-ray crystal structures of 5a,b establish the presence of coordination isomerism of the cyclopentadienyl ring, which at the same time strongly alters the characteristics of the P-N multiple bond. For 5a, η1-attachment of the Me5C5 moiety to the phosphorus and a localized phosphorus-carbon σ-bond are found, and the P-N double bond compares to that of alkylated iminophosphanes (rPN = 155.1 (8) pm). 5b exhibits η2-coordination of the cyclopentadienyl ring leading to increased P-N triple-bond character, as evidenced by shortening of the P-N distance (153.3 (3) pm) and the remarkable opening of the nitrogen valence angle (153.3 (2)°). The structure is discussed as an intramolecular π-complex between a formal cyclopentadienyl anion and an iminophosphenium cation. The 1H and 13C NMR spectra show that rapid elementotropic rearrangements around the five-membered ring take place both in solution and in the solid state. The unique temperature dependence of δ31P in solution together with the considerable differences in δ 31P between the solution and solid states are interpreted in a model assuming a "haptotropic" mechanism for the fluxionality involving dynamic η1/η2-coordination isomerizations in solution. As expected, nucleophilic displacement of the Me5C5 moiety takes place in the reaction of 5b,c with LiC6H2tBu3, yielding the iminophosphanes tBu3H2C6P=NR (R = Si-i-Pr3 (8b), SiMe3 (c)) as products. | en |
dc.language.iso | en | de |
dc.rights | info:eu-repo/semantics/openAccess | de |
dc.subject.classification | Iminophosphane , Isomer | de |
dc.subject.ddc | 540 | de |
dc.title | Coordination isomerism in pentamethylcyclopentadienyl-substituted iminophosphanes: from classical structures to a π-complexed iminophosphenium ion | en |
dc.type | article | de |
ubs.fakultaet | Fakultätsübergreifend / Sonstige Einrichtung | de |
ubs.institut | Sonstige Einrichtung | de |
ubs.opusid | 7433 | de |
ubs.publikation.source | Journal of the American Chemical Society 114 (1992), S. 8857-8862. URL http://dx.doi.org./10.1021/ja00049a018 | de |
ubs.publikation.typ | Zeitschriftenartikel | de |
Enthalten in den Sammlungen: | 15 Fakultätsübergreifend / Sonstige Einrichtung |
Dateien zu dieser Ressource:
Datei | Beschreibung | Größe | Format | |
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gud6.pdf | 1,62 MB | Adobe PDF | Öffnen/Anzeigen |
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