Hydrazinocarben-Metallkomplexe : Synthese aus Allenylidenkomplexen und Hydrazinen, Umlagerung und Cyclisierung

Kurzanzeige
dc.contributor.authorFischer, Helmut
dc.contributor.authorRoth, Gerharddeu
dc.date.accessioned2013-06-26T08:20:33Zdeu
dc.date.available2013-06-26T08:20:33Zdeu
dc.date.issued1995
dc.description.abstractThe diarylallenylidene pentacarbonyl complexes (CO)5M=C=C=C(C6H4NMe2-p)2 (M = W (1), Cr (2)) add 1,2,-disubstituted hydrazines RNH-HNR to form alkenyl hydrazino carbene complexes (CO)5M=C(C(H)=C(C6H4NMe2-p)2) NR-N(H)R (M = W, R = Bn (3b), iPr (3c), cHex (3d); M = Cr, R = Me (4a), iPr (4b)) in good yield. 3c and 4b are formed selectively as E-conformers (E arrangement of NβHR and (CO)5M with respect to the C(carbene)-Nα bond). In contrast, all other derivatives of 3 and 4 are obtained as a mixture of E/Z-isomers. On heating, E-3a and E-3b rearrange to give the acrylamidine complexes (CO)5W-NR=C(NHR)C(H)=C(C6H4NMe2-p)2 (R = Me (5a), Bn (5b). The structure of complex 5b was established by X-ray analysis. Acid-catalyzed, the alkenyl hydrazino carbene complexes E-3a, E-3b and 3c are transformed by intramolecular cyclization into the pyrazolidinylidene complexes (R =Me (6a), Bn (6b), iPr (6c)).eng
dc.description.versionpublished
dc.identifier.citationJournal of Organometallic Chemistry ; 490 (1995), 1-2. - S. 229-237deu
dc.identifier.doi10.1016/0022-328X(94)05187-Gdeu
dc.identifier.ppn384383823deu
dc.identifier.urihttp://kops.uni-konstanz.de/handle/123456789/23265
dc.language.isoengdeu
dc.legacy.dateIssued2013-06-26deu
dc.rightsterms-of-usedeu
dc.rights.urihttps://rightsstatements.org/page/InC/1.0/deu
dc.subjectAlkenylhydrazinocarbene complexesdeu
dc.subjectX-ray structure analysisdeu
dc.subjectRearrangementdeu
dc.subjectChromiumdeu
dc.subjectTungstendeu
dc.subject.ddc540deu
dc.titleHydrazinocarben-Metallkomplexe : Synthese aus Allenylidenkomplexen und Hydrazinen, Umlagerung und Cyclisierungeng
dc.typeJOURNAL_ARTICLEdeu
dspace.entity.typePublication
kops.citation.bibtex
@article{Fischer1995Hydra-23265,
  year={1995},
  doi={10.1016/0022-328X(94)05187-G},
  title={Hydrazinocarben-Metallkomplexe : Synthese aus Allenylidenkomplexen und Hydrazinen, Umlagerung und Cyclisierung},
  number={1-2},
  volume={490},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={229--237},
  author={Fischer, Helmut and Roth, Gerhard}
}
kops.citation.iso690FISCHER, Helmut, Gerhard ROTH, 1995. Hydrazinocarben-Metallkomplexe : Synthese aus Allenylidenkomplexen und Hydrazinen, Umlagerung und Cyclisierung. In: Journal of Organometallic Chemistry. 1995, 490(1-2), pp. 229-237. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(94)05187-Gdeu
kops.citation.iso690FISCHER, Helmut, Gerhard ROTH, 1995. Hydrazinocarben-Metallkomplexe : Synthese aus Allenylidenkomplexen und Hydrazinen, Umlagerung und Cyclisierung. In: Journal of Organometallic Chemistry. 1995, 490(1-2), pp. 229-237. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(94)05187-Geng
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    <dcterms:abstract xml:lang="eng">The diarylallenylidene pentacarbonyl complexes (CO)&lt;sub&gt;5&lt;/sub&gt;M=C=C=C(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;NMe&lt;sub&gt;2&lt;/sub&gt;-p)&lt;sub&gt;2&lt;/sub&gt; (M = W (1), Cr (2)) add 1,2,-disubstituted hydrazines RNH-HNR to form alkenyl hydrazino carbene complexes (CO)&lt;sub&gt;5&lt;/sub&gt;M=C(C(H)=C(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;NMe&lt;sub&gt;2&lt;/sub&gt;-p)&lt;sub&gt;2&lt;/sub&gt;) NR-N(H)R (M = W, R = Bn (3b), &lt;sup&gt;i&lt;/sup&gt;Pr (3c), &lt;sup&gt;c&lt;/sup&gt;Hex (3d); M = Cr, R = Me (4a), &lt;sup&gt;i&lt;/sup&gt;Pr (4b)) in good yield. 3c and 4b are formed selectively as E-conformers (E arrangement of N&lt;sub&gt;β&lt;/sub&gt;HR and (CO)&lt;sub&gt;5&lt;/sub&gt;M with respect to the C(carbene)-N&lt;sub&gt;α&lt;/sub&gt; bond). In contrast, all other derivatives of 3 and 4 are obtained as a mixture of E/Z-isomers. On heating, E-3a and E-3b rearrange to give the acrylamidine complexes (CO)&lt;sub&gt;5&lt;/sub&gt;W-NR=C(NHR)C(H)=C(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;NMe&lt;sub&gt;2&lt;/sub&gt;-p)&lt;sub&gt;2&lt;/sub&gt; (R = Me (5a), Bn (5b). The structure of complex 5b was established by X-ray analysis. Acid-catalyzed, the alkenyl hydrazino carbene complexes E-3a, E-3b and 3c are transformed by intramolecular cyclization into the pyrazolidinylidene complexes (R =Me (6a), Bn (6b), &lt;sup&gt;i&lt;/sup&gt;Pr (6c)).</dcterms:abstract>
    <dc:creator>Roth, Gerhard</dc:creator>
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kops.description.abstractDie Diarylallenyliden(pentacarbonyl)komplexe (CO)<sub>5</sub>M=C=C=C(C<sub>6</sub>H4NMe<sub>2</sub>-p)<sub>2</sub> (M = W (1), Cr (2)) addieren 1,2-disbustituierte Hydrazine RNH-HNR in guten Ausbeuten zu Alkenylhydrazinocarbenkomplexen (CO)<sub>5</sub>M=C(C(H)=C(C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>p)<sub>2</sub>) NR-N(H)R (M = W, R = Bn (3b), <sup>i</sup>Pr (3c), <sup>c</sup>Hex (3d); M = Cr, R =Me(4a), <sup>i</sup>Pr (4b)). 3c und 4b entstehen hierbei selektiv in der E-Konformation (E-Anordnung von N<sub>β</sub>HR und (CO)<sub>5</sub>M bezülich der C(Carben)-N<sub>α</sub>-Bindung). Alle anderen Derivate von 3 und 4 werden dagegen als E/Z-Isomerengemisch gebildet. E-3a und E-3b lagern sich beim Erwärmen in die Acrylamidinkomplexe (CO)<sub>5</sub>W-NR=C(NHR)C(H)=C(C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>-p)<sub>2</sub> (R = Me (5a), Bn (5b)) um. Die Struktur von 5b wurde anhand einer Röntgenstrukturanalyse gesichert. Säurekatalysiert cyclisieren die Alkenylhydrazinocarbenkomplexe E-3a, E-3b und 3c zu den Pyrazolidinylidenkomplexen (R = Me (6b), <sup>i</sup>Pr (6c)).deu
kops.description.openAccessopenaccessgreen
kops.flag.knbibliographyfalse
kops.identifier.nbnurn:nbn:de:bsz:352-232651deu
kops.sourcefieldJournal of Organometallic Chemistry. 1995, <b>490</b>(1-2), pp. 229-237. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(94)05187-Gdeu
kops.sourcefield.plainJournal of Organometallic Chemistry. 1995, 490(1-2), pp. 229-237. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(94)05187-Gdeu
kops.sourcefield.plainJournal of Organometallic Chemistry. 1995, 490(1-2), pp. 229-237. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(94)05187-Geng
kops.submitter.emailkarin.hoch@uni-konstanz.dedeu
relation.isAuthorOfPublication726c19aa-617a-4eb9-9a10-3747eff2ffc8
relation.isAuthorOfPublication.latestForDiscovery726c19aa-617a-4eb9-9a10-3747eff2ffc8
source.bibliographicInfo.fromPage229
source.bibliographicInfo.issue1-2
source.bibliographicInfo.toPage237
source.bibliographicInfo.volume490
source.identifier.issn0022-328X
source.periodicalTitleJournal of Organometallic Chemistry

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