Solid-state phosphorus-31 nuclear magnetic resonance and chlorine-35 nuclear quadrupole resonance studies of some alkyl- and aryl-chlorophosphoranes and their addition compounds with Lewis acids

The 31P n.m.r. and 35Cl n.q.r. spectra (where observable) of a number of solid methyl-, ethyl- and phenyl-chloro-phosphoranes and of their ionic 1 : 1 adducts with Lewis acids X, such as PCl5, SbCl5, BCl3, AlCl3, or ICl, have been recorded. The results show that the compounds PMenCl5–n, (1 ⩽n⩽3), PEt2Cl3, PEt3Cl2, and PPh3Cl2 have ionic structures of the type [PRnCl4–n]Cl in the solid state, whereas PPh2Cl3 and PPhCl4 are molecular. The adducts all have structures of the type [PRnCl4–n][XCl]. The symmetries of the species present are discussed.