4023-53-4Relevant articles and documents
Self-replication of tris(cyanoethyl)phosphine catalysed by platinum group metal complexes
Costa, Emiliana,Pringle, Paul G.,Smith, Martin B.,Worboys, Kerry
, p. 4277 - 4282 (2007/10/03)
The platinum(0) complex [Pt(tcep)3], tcep = P(CH2CH2CN)3, catalyses the formation of tcep from PH3 and CH2=CHCN. The complexes [M(tcep)3] (M = Pt, Pd or Ni) and [MCl(tcep)3] (M = Rh or Ir) are compared for their catalysis of the reaction of PH(CH2CH2CN)2 with CH2=CHCN to give tcep and it is shown that the platinum(0) complex is the most efficient. The platinum(0) catalysis has been studied in detail, monitoring the kinetics by 31P-{1H} NMR spectroscopy. It is revealed that the kinetics are a complex function of the concentration of product tcep. Qualitatively, the rates also depend on [CH2=CHCN] and [catalyst]. Both 31P-{1H} and 195Pt-{1H} NMR spectroscopy suggests that addition of CH2=CHCN to [Pt(tcep)3] gives the complex [Pt(tcep)2(η2-CH2=CHCN)] which undergoes phosphine exchange on the NMR time-scale. The binuclear complex [Pt2H2(tcep)2{η-P(CH2CH 2CN)2}2], formed upon addition of PH(CH2CH2CN)2 to trans-[PtHCl(tcep)2] in the presence of base, is shown to be a catalyst precursor for the reaction of PH(CH2CH2CN)2 with CH2=CHCN. Two parallel mechanisms involving mononuclear and binuclear intermediates are discussed to rationalise these observations.
Alkylation of phosphine PH3 generated from red phosphorus
Semenzin, Delphine,Etemad-Moghadam, Guita,Albouy, Dominique,Koenig, Max
, p. 3297 - 3300 (2007/10/02)
The generation of phosphine PH3 by alkaline hydrolysis of red phosphorus is realized. The subsequent alkylation of PH3 by terminal alkenes and alkynes in basic media leading to the corresponding aliphatic and vinylic phosphine derivatives can occur by two-steps or one-pot reaction by a Michael-like reaction mechanism.