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An iridium–SPO complex as bifunctional catalyst for the highly selective hydrogenation of aldehydes†
Catalysis Science & Technology ( IF 5 ) Pub Date : 2017-11-20 00:00:00 , DOI: 10.1039/c7cy01953j
Israel Cano 1, 2, 3, 4, 5 , Luis M. Martínez-Prieto 1, 2, 3, 4, 5 , Laure Vendier 6, 7, 7, 8, 9 , Piet W. N. M. van Leeuwen 1, 2, 3, 4, 5
Affiliation  

A secondary phosphine oxide (SPO) ligand (tert-butyl(phenyl)phosphine oxide) was employed to generate an Ir–SPO complex which shows a particular ability to activate dihydrogen under mild conditions without the help of an external base or additive. Such an iridium(I) complex serves as a precursor for homogeneous catalysis since under H2 it is converted to a mixture of several iridium(III) hydride species that are the active catalysts. This system was found to be a highly active catalyst for the hydrogenation of substituted aldehydes, giving very high conversions and chemoselectivities for a wide range of substrates. The SPO ligand presumably plays a key role in the catalytic process through heterolytic cleavage of H2 by metal–ligand cooperation. In addition, an exhaustive characterization of the different iridium hydride species was performed by 1D and 2D NMR spectroscopy. The oxidative addition of H2 to the Ir(I)–SPO complex is highly stereoselective, as all generated Ir(III) hydrides are homochiral. Finally, the crystal structure, as determined by X-ray diffraction, of a dinuclear iridium(III) hydride complex is described.

中文翻译:

铱-SPO络合物作为双官能催化剂,用于醛的高度选择性加氢

使用仲氧化膦(SPO)配体(丁基(苯基)氧化膦)生成Ir-SPO配合物,该配合物在温和条件下无需外部碱或添加剂的帮助下显示出激活二氢的特殊能力。这样的铱(I)络合物用作均相催化的前体,因为在H 2下将其转化为几种作为活性催化剂的氢化铱(III)物质的混合物。发现该系统是用于氢化取代醛的高活性催化剂,可为多种底物提供很高的转化率和化学选择性。SPO配体可能通过H 2的异质裂解在催化过程中起关键作用。通过金属-配体合作。另外,通过1D和2D NMR光谱对不同的氢化铱物质进行了详尽的表征。H 2在Ir(I)-SPO络合物中的氧化加成反应具有很高的立体选择性,因为所有生成的Ir(III)氢化物都是同手性的。最后,描述了通过X射线衍射确定的双核氢化铱(III)配合物的晶体结构。
更新日期:2017-11-20
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