Komplexchemische P4- und P2-Aktivierung bei Raumtemperatur

The novel phosphido complexes [thf(ArO)3W≡P→M(CO)5] (3 a,b; Ar=2,6‐Me2C6H3; M=W, Cr; 3 a is depicted here) can be prepared in high yields by the reaction of [W2(OAr)6] with tBuC≡P in the presence of [M(CO)5thf]. Initial reactivity studies with [(ArO)4W=O] and [(Ph3P)2Pt(η2‐C2H4)] resulted in the formation of dinuclear four‐membered ring complexes and indicated the high side‐on reactivity of these compounds. Theoretical studies of the model complexes [(HO)3W≡P], [(HO)3W≡P→W(CO)5], and [thf(HO)3W≡P→W(CO)5] give insights into the bonding situation.

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Novel Complexes with a Short Tungsten–Phosphorus Triple Bond

Kramkowski

Baum

Radius

et al. 1999

Chemistry A European J

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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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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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Synthese, Struktur und Reaktivität eines Diphosphadiferratetrahedrans mit einer Fe-Fe-Doppelbindung

Eichhorn¹,

Scherer²,

Sögding³

et al. 2001

Angew. Chem.

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Die Kurzzeitthermolyse des Schmetterlingsmoleküls [{Cp′′′(OC)2Fe}2P4] liefert neben [Cp′′′FeP5] und [{Cp′′′Fe}2P4] in 18 % Ausbeute das Diphosphadiferratetrahedran [{Cp′′′Fe}2(μ‐CO)(μ‐η2:η2‐P2)] mit einer Fe‐Fe‐Doppelbindung. Bei dessen Photolyse wird unter CO‐Eliminierung der P2‐Baustein in zwei μ‐P‐Liganden gespalten. Im gebildeten Zweikernkomplex 1, dessen 31P‐NMR‐Signal extrem tieffeldverschoben ist (δ=1406.9), steht der rautenförmige Fe2P2‐Vierring nahezu orthogonal zu den ekliptisch angeordneten Cp′′′‐Fünfringen (siehe Bild). Cp′′′=tBu3C5H2.

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Komplexchemische P4- und P2-Aktivierung bei Raumtemperatur

Cited by 17 publications

References 21 publications

Novel Complexes with a Short Tungsten–Phosphorus Triple Bond

Novel Complexes with a Short Tungsten–Phosphorus Triple Bond

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

Synthese, Struktur und Reaktivität eines Diphosphadiferratetrahedrans mit einer Fe-Fe-Doppelbindung

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