Allenylphosphonium Complexes of Rhodium and Iridium

作者：Cade Ian A; Colebatch Annie L; Hill Anthony F^*; Willis Anthony C

来源：Organometallics, 2014, 33(12): 3198-3204.

DOI：10.1021/om500450e

The propargylic salt [Ph3PCH2C equivalent to CH]PF6 ([1]PF6) undergoes a facile rearrangement to the allenyl isomer [Ph3PCH=C= CH2]PF6 ([2]PF6) upon coordination to rhodium and iridium. The eta(2)-allenylphosphonium salts [IrX(eta(2)-CH2=C=CHPPh3)(CO)(PPh3)(2)]PF6 (X = Cl, [4]PF6; X = Br, [5]PF6) and [RhCl(eta(2)-CH2=C=CHPPh3)-(PPh3)(2)]PF6 ([7]PF6) have been synthesized and characterized, including X-ray crystallographic analyses. In the case of rhodium, it was found that [7]PF6 was also formed by the reaction of the alpha-alkynylphosphonium salt [Ph3PC equivalent to CCH3]PF6 ([3]PF6) with [RhCl(PPh3)(3)]. The complex [RhCl(CO)(PPh3)(2)] was found to catalyze the isomerization of [1](+) to [2](+).

• 出版日期2014-6-23