Allenylphosphonium Complexes of Rhodium and Iridium

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• 作者：Ian A. Cade ; Annie L. Colebatch ; Anthony F. Hill ; Anthony C. Willis
• 刊名：Organometallics
• 出版年：2014
• 出版时间：June 23, 2014
• 年：2014
• 卷：33
• 期：12
• 页码：3198-3204
• 全文大小：365K
• ISSN：1520-6041

文摘

The propargylic salt [Ph₃PCH₂C鈮H]PF₆ ([1]PF₆) undergoes a facile rearrangement to the allenyl isomer [Ph₃PCH鈺怌鈺怌H₂]PF₆ ([2]PF₆) upon coordination to rhodium and iridium. The 畏²-allenylphosphonium salts [IrX(畏²-CH₂鈺怌鈺怌HPPh₃)(CO)(PPh₃)₂]PF₆ (X = Cl, [4]PF₆; X = Br, [5]PF₆) and [RhCl(畏²-CH₂鈺怌鈺怌HPPh₃)(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 伪-alkynylphosphonium salt [Ph₃PC鈮CH₃]PF₆ ([3]PF₆) with [RhCl(PPh₃)₃]. The complex [RhCl(CO)(PPh₃)₂] was found to catalyze the isomerization of [1]⁺ to [2]⁺.