An air-stable, primary alkylphosphine: FcCH2PH2 [Fc = (η5-C5H5)Fe(η5-C 5H4)]

Abstract

Sodium metabisulfite-mediated elimination of formaldehyde from the ferrocene-derived hydroxymethylphosphine FcCH 2 P(CH 2 OH) 2 yields the primary phosphine FcCH 2 PH 2 , which has been fully characterised, including an X-ray crystal structure; the phosphine is completely airstable.

From Racemic Primary Aminoalkyl(phosphanyl)ferrocene Complexes to a Lithium–Phosphorus closo Cluster

“…Upon addition of a small amount of a coordinating solvent, such as more THF, a second sharp signal at d = À177.3 ppm is observed, and, in THF alone, only this signal is observed, which we believe is due to the solventseparated ion pairs of the dilithium phosphinediide. A similar phenomenon was revealed by 7 Li NMR spectroscopy investigations. A solution of 5 in n-hexane that contains a few drops of THF shows a broad multiplet for the Li 12 P 6 cluster at d = 0.7-5.1 ppm, this multiplet consists of several overlapping signals, and a small singlet at d = 0.5 ppm for the dilithium phosphinediide.…”

“…31 P and 7 Li NMR spectroscopy studies show that the structure of the Li 12 P 6 cluster in solution is solvent-dependent. In nonpolar solvents, such as n-hexane, compound 5 is hardly soluble, but it dissolves when few drops of THF are added.…”

“…[6] Both compounds are unstable when exposed to air and are oxidized within a few days in the solid state, and within a few seconds in solution. Primary phosphanylalkylferrocene complexes that have a methylene or ethylene bridge between the ferrocene moiety and the phosphanyl group are much more stable, these compounds include (phosphanylmethyl)ferrocene, [7] 1,1'-bis(phosphanylmethyl)ferrocene, 1,2-bis(phosphanylmethyl)ferrocene, and 1-phosphanyl-2-ferrocenylethane. [8] The reactivity of the PÀH bonds offers great synthetic potential.…”

Von racemischen primären Aminoalkyl(phosphanyl)ferrocenen zu einem Lithium‐Phosphor‐closo‐Cluster

“…[6] Beide Verbindungen sind luftempfindlich und zersetzen sich in Lösung innerhalb weniger Sekunden, als Festkörper in einigen Tagen. Primäre Phosphanylalkylferrocene, in denen die Ferrocenyl-und die Phosphanylgruppe durch eine Methylen-oder Ethylenbrücke verbunden sind, wie (Phosphanylmethyl)ferrocen, [7] 1,1'-Bis(phosphanylmethyl)ferrocen, 1,2-Bis(phosphanylmethyl)ferrocen und 1-Phosphanyl-2-ferrocenylethan, [8] sind hingegen erheblich luftstabiler. Die Reaktivität der P-H-Bindung bietet zahlreiche Perspektiven für die Synthese.…”

Synthesis and X-ray crystal structure of [2-(phosphinomethyl)ferrocenyl]diphenylphosphine

“…They are however also typically air-sensitive, often pyrophoric and, thus, difficult compounds to handle. Recent work from W. Henderson [1,2,3] pointed out the availability of especially 'user-friendly' primary phosphines which incorporates ferrocenyl groups, i.e. ferrocenylmethyl-and ferrocenylethylphosphines 1.…”