Combined Experimental/Computational Study of Iridium and Palladium Hydride PP(O)P Pincer Complexes

详细信息    查看全文

• 作者：Carmen Martin ; Sonia Mallet-Ladeira ; Karinne Miqueu ; Ghenwa Bouhadir ; Didier Bourissou
• 刊名：Organometallics
• 出版年：2014
• 出版时间：January 27, 2014
• 年：2014
• 卷：33
• 期：2
• 页码：571-577
• 全文大小：309K
• ISSN：1520-6041

文摘

The diphosphine鈥損hosphine oxide {[o-iPr₂P(C₆H₄)]₂P(鈺怬)H} (1) has been prepared, and its coordination to Ir and Pd has been explored. Using [IrCl(cyclooctene)₂]₂, the pincer hydride complex {(o-iPr₂PC₆H₄)₂P(O)]IrHCl} (2) is readily obtained by phosphine-assisted P(O)鈥揌 bond activation. Coordination of CO to Ir affords the corresponding octahedral complex {(o-iPr₂PC₆H₄)₂P(O)]IrHCl(CO)} (3) as a single stereoisomer. The electronic properties of the PP(O)P ligand have been compared with those of related PEP frameworks on the basis of 谓_CO stretching frequencies. Treatment of 1 with [Pd(PtBu₃)₂] gives the palladium hydride complex {(o-iPr₂PC₆H₄)₂P(O)]PdH} (4). The mechanism of P(O)鈥揌 bond activation at Pd has been investigated computationally. Complex 4 reacts with methyl acrylate at room temperature, giving {(o-iPr₂PC₆H₄)₂P(O)]PdCH(Me)CO₂Me} (7) as the result of regioselective insertion into the Pd鈥揌 bond.