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–.