[Ru(triphos)(CH3CN)3](OTf)2 as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium
[Ru(triphos)(CH3CN)3](OTf)2 as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium
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DOI：
10.1039/c7gc01956d
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发表时间：
2017-10-07
期刊：
影响因子：
9.8
通讯作者：
Schlaf, Marcel
中科院分区：
文献类型：
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作者：
Latifi, Elnaz;Marchese, Austin D.;Schlaf, Marcel
络合物[Ru（triphos）（CH 3 CN）（3）]（OTf）（2）是用于在150 - 200 ℃的温度下在酸性水介质中氢化2，5-己二酮和2，5-二甲基-呋喃的有效催化剂，实现高达96%的2，5-己二醇和2，5-二甲基-四氢呋喃，产物分布对存在的酸助催化剂（HOTf）的量敏感。对于呋喃，反应途径是通过酸催化水解成二酮，而不是环的直接氢化。二酮的氢化显示出一级依赖于氢压力，如通过在温度和压力下直接氢吸收速率测量所确定的（1.38-6.90 MPa，150 ℃），并假定通过[Ru（H）（x）（triphos）（Y）（y）]（n+）对氢气的异裂活化来操作。（y=溶剂、水、抗衡离子）通过腈配体的损失和氢化原位形成的物质。在水中，催化剂通过二聚作用失活为[Ru-2（mu-OH）（3）（triphos）（2）]（OTf）。
The complex [Ru(triphos)(CH3CN)(3)](OTf)(2) is an effective catalyst for the hydrogenation of 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium at temperatures between 150 and 200 degrees C realizing up to 96% combined yields of 2,5-hexanediol and 2,5-dimethyl-tetrahydrofuran with the product distribution being sensitive to the amount of acid co-catalyst (HOTf) present. For the furan, the reaction pathway is through an acid-catalyzed hydrolysis to the dione rather than direct hydrogenation of the ring. The hydrogenation of the dione shows a first order dependence on hydrogen pressure as determined by direct hydrogen uptake rate measurements at temperature and pressure (1.38-6.90 MPa at 150 degrees C) and is postulated to operate through a heterolytic activation of hydrogen gas by [Ru(H)(x)(triphos)(Y)(y)](n+) (y=solvent, water, counter ion) species formed in situ by loss and hydrogenation of the nitrile ligands. In water the catalyst is deactivated by dimerization to [Ru-2(mu-OH)(3)(triphos)(2)](OTf).