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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A novel dicationic phenoxaphosphino-modified Xantphos-type ligand:a ligand for highly active and selective,biphasic,rhodium catalysed hydroformylation in ionic liquids
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A novel dicationic phenoxaphosphino-modified Xantphos-type ligand:a ligand for highly active and selective,biphasic,rhodium catalysed hydroformylation in ionic liquids

机译:一种新型的离子型苯氧磷膦修饰的Xantphos型配体:用于离子液体中高活性和选择性,双相,铑催化的加氢甲酰化的配体

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摘要

A highly active and regioselective catalyst obtained from a novel dicationic ligand (1) and Rh(CO)_2(acac) for hydroformylation of 1-hexene and 1-octene in ionic liquids is reported. Optimisation studies of various reaction parameters led to an unprecedentedly active (TOFs > 6200 mol mol~(-1) h~(-1), T = 100 degC), selective (1/b ratios > 40) and stable hydroformylation procedure. No catalyst leaching (Rh-loss < 0.07% of initial rhodium intake, P-loss < 0.4% of the initial phosphorus intake) or losses in performance could be measured during 1-octene hydroformylation recycle experiments in l-butyl-3-methylimidazolium hexafluorophosphate. At low catalyst loadings activities and regioselectivities competitive with one-phase catalysis in conventional solvents were observed. At high catalyst loadings the system is extremely stable and has a long shelf-life as a result of the formation of stable, if inactive rhodium dimers.
机译:报道了一种由新型的二元配体(1)和Rh(CO)_2(acac)制备的高活性和区域选择性催化剂,用于离子液体中1-己烯和1-辛烯的加氢甲酰化。对各种反应参数的优化研究导致了前所未有的活性(TOF> 6200 mol mol〜(-1)h〜(-1),T = 100℃),选择性(1 / b比> 40)和稳定的加氢甲酰化程序。在1-丁基-3-甲基咪唑六氟磷酸盐的1-辛烯加氢甲酰化循环实验中,无法测量出催化剂的浸出(Rh损失<初始铑摄入量的0.07%,P损失<初始磷摄入量的0.4%)或性能损失。在低催化剂负载下,观察到活性和区域选择性与常规溶剂中的一相催化竞争。在高催化剂负载下,由于形成稳定的铑二聚体(如果没有活性),该系统极其稳定,并且具有较长的保存期限。

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