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

Fischer, Helmut; Reindl, David; Troll, Carsten; Leroux, Frédéric

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

Files

Fischer_Reindl_etal.pdf(1.37 MB)

Date

1995

Authors

Fischer, Helmut

Reindl, David

Troll, Carsten

Leroux, Frédéric

Publication type

Journal article

Published in

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 C_α 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 C_α 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 C_α-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 C_α-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

Cite This

ISO 690

FISCHER, 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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