Allenylphosphonium Complexes of Rhodium and Iridium
2014-06-23T00:00:00Z (GMT) by
The propargylic salt [Ph3PCH2CCH]PF6 (PF6) undergoes a facile rearrangement to the allenyl isomer [Ph3PCHCCH2]PF6 (PF6) upon coordination to rhodium and iridium. The η2-allenylphosphonium salts [IrX(η2-CH2CCHPPh3)(CO)(PPh3)2]PF6 (X = Cl, PF6; X = Br, PF6) and [RhCl(η2-CH2CCHPPh3)(PPh3)2]PF6 (PF6) have been synthesized and characterized, including X-ray crystallographic analyses. In the case of rhodium, it was found that PF6 was also formed by the reaction of the α-alkynylphosphonium salt [Ph3PCCCH3]PF6 (PF6) with [RhCl(PPh3)3]. The complex [RhCl(CO)(PPh3)2] was found to catalyze the isomerization of + to +.