CONVERSION OF ALLYLPHOSPHINE TO NOVEL DIPHOSPHINES: SYNTHESIS AND CHARACTERIZATION OF CH2=CHCH2P(H)(CH2)3PH2AND P[(CH2)3]3P1

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Abstract Irradiation (λ = 300–600 nm) of gaseous CH2=CHCH2PH2 in a hot-cold reactor yields the new diphosphine, CH2=CHCH2P(H)(CH2)3PH2(I). I results from the intermolecular head-to-tail addition of phosphine PH bonds to the C=C bonds of CH2=CHCH2PH2, in an anti-Markovnikov process. The AIBN-initiated radical reaction of CH2=CHCH2PH2 in benzene yields PH3 and the novel bicyclic diphosphine, P[(CH2)3]3P(II). Characterization of I and II, based on 31P, 1H, and 13C NMR and mass spectral data, is described.