SYNTHESIS, REACTIONS AND CATALYTIC ACTIVITIES OF SIGMA AND ETA-3-ALLYL-BIS(TRIPHENYLSTIBINE)RHODIUM(III) COMPLEXES

Reaction of [RhCl(CO)(SbPh3)2] 1 with CH2 = CHCH2Br 2a gives the sigma-allylrhodium(III) complex [Rh(sigma-CH2CH = CH2)Cl(Br)(CO)(SbPh3)2] 3, while reactions of 1 with allyl halides and AgClO4 give eta-3-allylrhodium(III) complexes [Rh(eta-3-allyl)X(CO) (SbPh3)2] ClO4 4 [allyl = CH2CHCH2, CH2CHCHMe (X = Br or Cl), CH2CMeCH2, or CH2CHCHPh (X = Cl)]. The complex [Rh(eta-3-CH2CHCH2)Br(CO)-(SbPh3)2]ClO4 can also be prepared by the reaction of 3 with AgClO4. The complex [Rh(eta-3-CH2-CHCH2)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 eta-3-allyl complexes 4 in the presence of ClO4-.