[Os(η2-PHS)(CO)2(PPh3)2], ein stabiler η2-Thioxophosphan(HPS)-Metallkomplex

An overview of the chemistry of transition metal complexes containing P−H bonds is presented. Central to this microreview are those compounds in which the P−H bond is assembled by reactions entailing the transfer of one or more hydrogen atoms to white phosphorus or to Px fragments resulting from P4 activation and degradation within the coordination sphere of a transition metal complex. The relevance of these processes to the as yet unaccomplished hydrogenation of white phosphorus is briefly discussed.

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Metal-Assisted P−H Bond Formation: A Step towards the Hydrogenation of White Phosphorus

Peruzzini¹,

Ríos²,

Romerosa

et al. 2001

Eur. J. Inorg. Chem.

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Neue Zwischenstufen der Cyclocotrimerisierung von Thioxophosphor(V)‐Kationen mit Alkinen

et al. 1989

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Ein Thiaphosphametallacyclopropan und ein Thiaphosphametallacycloheptadien sind die neuen für das Verständnis des Mechanismus der Cyclocotrimerisierung von Thioxophosphor(V)‐Kationen und Alkinen wichtigen Verbindungen. Sie wurden durch Verwendung eines sperrigen Substituenten R am Phosphoratom zugänglich. Die Verbindungen 2 entstehen aus dem Metallacyclopropan 1 und Methyl‐ oder Ethylacetylendicarboxylat in Hexan. Beim Erhitzen in THF gehen sie unter CO‐Abspaltung in die bekannten Metallabicycloheptadiene 3 über. R1 = Cyclohexyl; R2 = CO2Me, CO2Et.

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New Intermediates in the Cyclocotrimerization of Thioxophosphorus(V) Cations with Alkynes

Lindner

Käss

Hiller

et al. 1989

Angew. Chem. Int. Ed. Engl.

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A thiaphosphametallacyclopropane and a thiaphosphametallacycloheptadiene are important intermediates for understanding the mechanism of the cyclotrimerization of thioxophosphorus(V) cations and alkynes. These species are accessible by use of a bulky substituent R at the phosphorus atom. Compounds 2 are formed from the metallacyclopropane 1 and dimethyl or diethyl acetylenedicarboxylate in hexane. Upon heating in THF, they lose CO and are transformed into the known metallabicycloheptadienes 3. R1 = cyclohexyl; R2 = CO2Me, CO2Et.

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[Os(η2-PHS)(CO)2(PPh3)2], ein stabiler η2-Thioxophosphan(HPS)-Metallkomplex

Cited by 8 publications

References 15 publications

Metal-Assisted P−H Bond Formation: A Step towards the Hydrogenation of White Phosphorus

Metal-Assisted P−H Bond Formation: A Step towards the Hydrogenation of White Phosphorus

Neue Zwischenstufen der Cyclocotrimerisierung von Thioxophosphor(V)‐Kationen mit Alkinen

New Intermediates in the Cyclocotrimerization of Thioxophosphorus(V) Cations with Alkynes

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