CH(2) Linkage Effects on the Reactivity of Bis(aminophosphine)-Ruthenium Complexes for Selective Hydrogenation of Esters into Alcohols.
CH(2) Linkage Effects on the Reactivity of Bis(aminophosphine)-Ruthenium Complexes for Selective Hydrogenation of Esters into Alcohols.
复制标题
CH2 连接对双(氨基膦)-钌配合物选择性加氢酯成醇反应活性的影响
DOI：
10.1038/s41598-017-04362-9
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发表时间：
2017-06-21
影响因子：
4.6
通讯作者：
Yuan Y
中科院分区：
文献类型：
--
作者：
Fang X;Sun M;Zheng J;Li B;Ye L;Wang X;Cao Z;Zhu H;Yuan Y
成功地分离出了一个与两种不同的氨基膦配体(o-PPh2C6H4CH2NH2)(o-PPh2C6H4NH2)RuCl2结合的新型Ru配合物。这种双(氨基膦)-Ru络合物在草酸二甲酯(DMO)和苯甲酸甲酯(MB)加氢反应中表现出有效的活性。相反，类似的配合物(o-PPh2C6H4NH2)2RuCl2和(o-PPh2C6H4CH2NH2)2RuCl2只能有效地催化DMO和MB的加氢反应。我们的实验研究结合理论计算表明，在酯的加氢反应中，显着的底物选择性源于配体CH2键的非键相互作用。
A novel ruthenium complex binding to two subtly different aminophosphine ligands, (o-PPh2C6H4CH2NH2)(o-PPh2C6H4NH2)RuCl2, was successfully isolated. This bis(aminophosphine)–ruthenium complex shows efficient activity in both dimethyl oxalate (DMO) and methyl benzoate (MB) hydrogenation. On the contrast, similar complexes (o-PPh2C6H4NH2)2RuCl2 and (o-PPh2C6H4CH2NH2)2RuCl2, can only effectively catalyze the hydrogenation of DMO and MB, respectively. Our experimental studies in combination of theoretical calculations reveal that the remarkable substrate selectivity in the hydrogenation of esters arises from the nonbonding interactions operated by the CH2 linkage of the ligand.