Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe

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1995
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Reindl, David
Troll, Carsten
Leroux, Frédéric
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Journal of Organometallic Chemistry ; 490 (1995), 1-2. - pp. 221-227. - ISSN 0022-328X
Abstract
The allenylidene(pentacarbonyl)chromium complex (CO)5Cr[C=C=C(C6H4NMe2-p)2] (1a) adds phosphines PR3 at the Cα atom to give ylide complexes, (CO)5Cr-[C(PR3=C=C(C6H4NMe2-p)2] (PR3 = PMe3 (3), PHPh2 (3), PH2Mes (7) (Mes = C6H2Me3-2,4,6)). At room temperature complex 3 slowly rearranges to the allenylphosphine complex (CO)5Cr-PPh2[CH=C=C(C6H4NMe2-p)2] (4). The structure of 4 was established by an X-ray structure analysis. The adduct 7 obtained from 1a and PH2Mes, however, could not be detected. It immediately isomerizes to the alkynylphosphine complex (CO)5Cr-PH(Mes)[C≡C-CH(C6H4NMe2-p)2] (8). At room temperature the ylide complex 5, formed by addition of PHPh2 to the Cα atom of the allenylidene complex (CO)5Cr=C=C=C(o-C6H4)2O (1b), rearranges in CH2Cl2 in the presence of excess PHPh2 to give a binuclear bisphosphine complex (6). 6 corresponds to the product of the chemo-, regio- and stereo-selective dimerization of the allenylphosphine complex analogous to 4.
Summary in another language
Der Allenyliden(pentacarbonyl)chrom-Komplex (CO)5Cr[C=C=C(C6H4NMe2-p)2] (1a) addiert Phosphane PR3 am Cα-Atom unter Bildung von Ylid--Komplexen, (CO)5Cr-[C(PR3)=C=C(C6H4NMe2-p)2](PR3 = PMe3 (2), PHPh2 (3), PH2Mes (7) (Mes = C6H2Me3-2,4,6)). Bei Raumtemperatur lagert sich der Komplex 3 langsam in den Allenylphosphan-Komplex (CO)5Cr-PPh2[CH=C=C(C6H4NMe2-p)2] (4) um. Die Struktur von 4 wurd durch eine Röntgenstrukturanalyse gesichert. Das Addukt 7 aus 1a und PH2Mes konnte nicht nachgewiesen werden, es isomerisiert sofort zum Alkinylphosphan-Komplex (CO)5Cr-PH(Mes)[C≡C-CH(C6H4NMe2-p)2] (8). Der Ylid-Komplex 5, der durch Addition von PHPh2 an das Cα-ATom des Allenyliden-Komplex s (CO)5Cr=C=C=C(o-C6H4)2O (1b) entsteht, lagert sich bei Raumtemperatur in CH2Cl2 in Gegenwart von PHPh2 im Überschuß in einen zweikernigen Bisphosphan-Komplex (6) um. Dieser entspricht dem Produkt einer chemo-, regio- und stereoselektiven Dimerisierung des zu 4 analogen Allenylphosphan-Komplexes.
Subject (DDC)
540 Chemistry
Keywords
Chromium,Phosphane complexes,Allenylidene complexes,Nucleophilic addition,Ylide complexes
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Cite This
ISO 690FISCHER, Helmut, David REINDL, Carsten TROLL, Frédéric LEROUX, 1995. Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe. In: Journal of Organometallic Chemistry. 490(1-2), pp. 221-227. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(94)05210-3
BibTex
@article{Fischer1995Addit-23266,
  year={1995},
  doi={10.1016/0022-328X(94)05210-3},
  title={Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe},
  number={1-2},
  volume={490},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={221--227},
  author={Fischer, Helmut and Reindl, David and Troll, Carsten and Leroux, Frédéric}
}
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    <dcterms:abstract xml:lang="eng">The allenylidene(pentacarbonyl)chromium complex (CO)&lt;sub&gt;5&lt;/sub&gt;Cr[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;] (1a) adds phosphines PR&lt;sub&gt;3&lt;/sub&gt; at the C&lt;sub&gt;α&lt;/sub&gt; atom to give ylide complexes, (CO)&lt;sub&gt;5&lt;/sub&gt;Cr-[C(PR&lt;sub&gt;3&lt;/sub&gt;=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;] (PR&lt;sub&gt;3&lt;/sub&gt; = PMe&lt;sub&gt;3&lt;/sub&gt; (3), PHPh&lt;sub&gt;2&lt;/sub&gt; (3), PH&lt;sub&gt;2&lt;/sub&gt;Mes (7) (Mes = C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;Me3-2,4,6)). At room temperature complex 3 slowly rearranges to the allenylphosphine complex (CO)&lt;sub&gt;5&lt;/sub&gt;Cr-PPh&lt;sub&gt;2&lt;/sub&gt;[CH=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;] (4). The structure of 4 was established by an X-ray structure analysis. The adduct 7 obtained from 1a and PH&lt;sub&gt;2&lt;/sub&gt;Mes, however, could not be detected. It immediately isomerizes to the alkynylphosphine complex (CO)&lt;sub&gt;5&lt;/sub&gt;Cr-PH(Mes)[C≡C-CH(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;] (8). At room temperature the ylide complex 5, formed by addition of PHPh2 to the C&lt;sub&gt;α&lt;/sub&gt; atom of the allenylidene complex (CO)&lt;sub&gt;5&lt;/sub&gt;Cr=C=C=C(o-C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;O (1b), rearranges in CH&lt;sub&gt;2&lt;/sub&gt;Cl&lt;sub&gt;2&lt;/sub&gt; in the presence of excess PHPh&lt;sub&gt;2&lt;/sub&gt; to give a binuclear bisphosphine complex (6). 6 corresponds to the product of the chemo-, regio- and stereo-selective dimerization of the allenylphosphine complex analogous to 4.</dcterms:abstract>
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