Stereoelectronic and Catalytic Properties of Chiral Cyclometalated Phospha-palladium and -platinum Complexes

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• 作者：Yu-Xiang Jia ; Bin-Bin Li ; Yongxin Li ; Sumod A. Pullarkat ; Kai Xu ; Hajime Hirao ; Pak-Hing Leung
• 刊名：Organometallics
• 出版年：2014
• 出版时间：November 10, 2014
• 年：2014
• 卷：33
• 期：21
• 页码：6053-6058
• 全文大小：319K
• ISSN：1520-6041

文摘

The stereoelectronic properties of palladium(II) and platinum(II) complexes containing ortho-metalated (1-(diphenylphosphino)ethyl)naphthalene were examined by X-ray crystallography in the solid state and by NMR spectroscopy in solution. The studies revealed that the aromatic carbon induced a significantly stronger electronic trans-influence than the phosphorus donor within the same five-membered chelate. Both the organopalladium and organoplatinum chelate complexes were formed with classical hard oxygen and soft phosphorus donor atoms. Computational studies further confirmed the observations in the solid state and solution that the C鈥搈etal bond in the trans C鈥揚t鈥揙 moiety has a stronger 蟺-character than that in the trans C鈥揚t鈥揚 moiety. Both organometallic units are efficient catalysts for the asymmetric P鈥揌 addition reaction. They showed almost identical efficiency in dichloromethane, but their reactivity in THF is markedly different.