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- W2059280385 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. 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." @default.
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- W2059280385 date "1995-03-01" @default.
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- W2059280385 title "Addition von Phosphanen an das Cα-Atom von allenyliden(pentacarbonyl)chrom und umlagerung in phosphan-komplexe" @default.
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- W2059280385 doi "https://doi.org/10.1016/0022-328x(94)05210-3" @default.
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