We report a variety of manganese-based catalysts containing both chelating diphosphine (bis(diphenylphosphino)methane (dppm: 1, 2, and 7) or 1,2-bis(diphenylphosphino)ethane (dppe: 3)), and mixed-donor phosphinoamine (2-(diphenylphosphino)ethylamine (dppea: 4–6)) ligands for the upgrading of ethanol and methanol to the advanced biofuel isobutanol. These catalysts show moderate selectivity up to 74% along with turnover numbers greater than 100 over 90 h, with catalyst 2 supported by dppm demonstrating superior performance. The positive effect of substituting the ligand backbone was also displayed with a catalyst supported by C-phenyl-substituted dppm (8) having markedly improved performance compared to the parent dppm catalysts. Catalysts supported by the phosphinoamine ligand dppea are also active for the upgrading of ethanol to n-butanol. These results show that so-called PNP-pincer ligands are not a prerequisite for the use of manganese catalysts in Guerbet chemistry and that simple chelates can be used effectively.

中文翻译：

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锰二膦和膦胺配合物是通过Guerbet反应生产生物燃料醇的有效催化剂

我们报告了各种含有螯合二膦（双（二苯基膦基）甲烷（DPPM：基于锰的催化剂的1，2，和7）或1,2-双（二苯基膦基）乙烷（dppe：3）），和混合供体膦胺（2-（二苯基膦基）乙胺（dppea：4 – 6））配体，用于将乙醇和甲醇升级为高级生物燃料异丁醇。这些催化剂显示出高达74％的中等选择性，并且在90小时内的转化率大于100，其中dppm负载的催化剂2表现出优异的性能。取代基配体主链的积极作用还体现在C-苯基取代的dppm（8）与母体dppm催化剂相比具有显着改善的性能。膦胺配体dppea负载的催化剂对于将乙醇升级为正丁醇也具有活性。这些结果表明，所谓的PNP-夹子配体不是在Guerbet化学中使用锰催化剂的先决条件，并且可以有效地使用简单的螯合物。