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

Abstract

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 PMe_nCl_5–n, (1 ⩽n⩽3), PEt₂Cl₃, PEt₃Cl₂, and PPh₃Cl₂ have ionic structures of the type [PR_nCl_4–n]Cl in the solid state, whereas PPh₂Cl₃ and PPhCl₄ are molecular. The adducts all have structures of the type [PR_nCl_4–n][XCl]. The symmetries of the species present are discussed.