Synthesis, reactions and catalytic activities of σ- and η3-allyl-bis(triphenylstibine)rhodium(III) complexes

Abstract

Reaction of [RhCl(CO)(SbPh₃)₂]1 with CH₂CHCH₂Br 2a gives the σ-allylrhodium(III) complex [Rh(σ-CH₂CHCH₂)Cl(Br)(CO)(SbPh₃)₂]3, while reactions of 1 with allyl halides and AgClO₄ give η³-allylrhodium(III) complexes [Rh(η³-allyl)X(CO)(SbPh₃)₂]ClO₄4[allyl = CH₂CHCH₂, CH₂CHCHMe (X = Br or Cl), CH₂CMeCH₂, or CH₂CHCHPh (X = Cl)]. The complex [Rh(η³-CH₂CHCH₂)Br(CO)(SbPh₃)₂]ClO₄ can also be prepared by the reaction of 3 with AgClO₄. The complex [Rh(η³-CH₂CHCH₂)Cl(CO)(SbPh₃)₂]ClO₄ reacts with alcohols, amines and triphenylphosphine to give 1 and allyl ethers, diallylamines and allylphosphonium perchlorate, respectively. Reactions of allyl halides with alcohols and amines are catalysed by the η³-allyl complexes 4 in the presence of ClO₄^–.