Sol-Gel Processed Diamine(diphosphine)ruthenium(II) Complexes for the Catalytic Hydrogenation of , 详细信息    查看全文

• 作者：Da-Yong Wu ; Ekkehard Lindner ; Hermann A. Mayer ; Zheng-Jin Jiang ; Venkata Krishnan ; and Helmut Bertagnolli
• 刊名：Chemistry of Materials
• 出版年：2005
• 出版时间：July 26, 2005
• 年：2005
• 卷：17
• 期：15
• 页码：3951 - 3959
• 全文大小：120K
• 年卷期：v.17,no.15(July 26, 2005)
• ISSN：1520-5002

文摘

Diphenyldiphosphinopropane 4T⁰, provided with a T⁰-silyl functionalized (CH₂)₆-spacer in the symmetric2-position of the C3 bridge, was obtained via an improved synthetic route in high yields, starting from8-chloro-7-chloromethyl-1-octene (1) (Scheme 1). Reaction of 4T⁰ with trans-RuCl₂(NBD)Py₂ in CH₂Cl₂resulted in the formation of the corresponding (diphos)ruthenium(II) complex 5T⁰ (Scheme 2), which,by treatment with 1,2-diaminopropane, was transformed to the T⁰-silyl functionalized diamine(diphosphine)ruthenium(II) complex 6T⁰. In the presence of four different amounts of the co-condensationagent MeSi(OMe)₃, 6T⁰ was subjected to a sol-gel process (Scheme 3). The resulting inorganic/organichybrid materials X1-X4 [6T⁰/MeSi(OMe)₃ = 1:10/15/20/50] were characterized by ³¹P and ²⁹Si solid-state NMR and EXAFS spectroscopy, as well as by EDX and BET measurements. It was confirmed thatthe integrity of the organometallic centers in X1-X4 is maintained compared to the monomeric counterpart6T⁰. The materials X1-X4 proved to be catalytically active in the direct hydrogenation of the modelsubstrate trans-4-phenyl-3-butene-2-one. With a conversion rate of 100% and a selectivity to the alcoholA (Scheme 4) of approximately 91%, the interphase catalyst X1 showed the best performance. It couldbe recovered eight times without detectable leaching and remarkable deactivation. The catalytic activitiesof X1 and monomeric 6T⁰ were compared with each other.