Camphene-derived primary and hydroxymethyl phosphines

Thermal disproportionation of (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)ph osphinic acid (endo-8-camphanylphosphinic acid, camPO(2)H(2)) yields the pr imary phosphine (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)phosphine (camPH (2)). The compound has been characterised by NMR spectroscopy, and as its t ris(hydroxymethyl)phosphonium chloride salt [camP(CH2OH)(3)]Cl, synthesised by reaction with excess formaldehyde and hydrochloric acid. The X-ray crys tal structure of this phosphonium salt is reported, confirming the endo pos ition of the phosphonium group. On treatment with triethylamine base, camP( CH2OH)(3)Cl-+(-) is converted to the hydroxymethylphosphine camP(CH2OH)(2). The sulfide and selenide of this phosphine have been prepared, together wi th the platinum(ii) complex cis-[PtCl2{camP(CH2OH)(2)}(2)]. The gas-phase d ecomposition of camPH(2) has been investigated using the technique of IR la ser powered homogeneous pyrolysis. Results indicate the initial elimination of phosphine, followed by the rearrangement and decomposition of camphene through two distinct pathways.