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首页> 外文期刊>Chemistry: A European journal >Acid-, Water- and High-Temperature-Stable Ruthenium Complexes for theTotal Catalytic Deoxygenation of Glycerol to Propane
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Acid-, Water- and High-Temperature-Stable Ruthenium Complexes for theTotal Catalytic Deoxygenation of Glycerol to Propane

机译：酸，水和高温稳定的钌配合物，用于甘油催化完全氧化为丙烷

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摘要

The ruthenium aqua com-plexes [Ru(H20)2(biPY)2](0T02, [cis-Ru(6,6'-C12-bipy)2(OH2)21(0T02, [Ru- (1120)2(flhen)21(0T02,[Ru- (H20)3(2,2':6',2"-terPM(OTO2and [Ru(H20)3(PhterPY)i(OTO2 (biPY=2,2'-bipyridine; OTf- =triflate; phen =phenanthroline; terpy = terpyridine;Phterpy = 4'-phenyl-2,2':6',2"-terpyri- dine) are water- and acid-stable cata-lysts for the hydrogenation of alde-hydes and ketones in sulfolane solu-tion. In the presence of HOS(0)2CF3(triflic acid) as a dehydration co-cata-lyst they directly convert 1,2-hexane- diol to n-hexanol and hexane. The ter-pyridine complexes are stable andactive as catalysts at temperatures^250°C and in either aqueous sulfo-lane solution or pure water convertglycerol into n-propanol and ultimatelypropane as the final reaction productin up to quantitative yield. For theterpy complexes the active catalyst ispostulated to be a carbonyl species [(4'-R-2,2':6',2"-terpy)Ru(C0)(H20)21-(0TH, (R=H, Ph) formed by the de-carbonylation of aldehydes (hexanalfor 1,2-hexanediol and 3-hydroxypro-panal for glycerol) generated in the re-action mixture through acid-catalyzeddehydration. The structure of the di-meric complex [{(4'-pheny1-2,2':6',2"-terpy)Ru(C0)12(11-0CH,)21(0TH2 hasbeen determined by single crystal X-ray crystallography (Space group P1 (a= 8.2532(17);b= 12.858(3);c=14.363(3) A; a = 64.38(3); /3= 77.26(3);y = 87.12(3)°, R=4.36%).
机译：钌水络合物[Ru（H20）2（biPY）2]（0T02，[cis-Ru（6,6'-C12-bipy）2（OH2）21（0T02，[Ru-（1120）2（ flhen）21（0T02，[Ru-（H20）3（2,2'：6'，2“ -terPM（OTO2和[Ru（H20）3（PhterPY）i（OTO2（biPY = 2,2'-联吡啶）; OTf- =三氟甲磺酸盐; phen =邻菲咯啉; terpy =联吡啶; Phterpy = 4'-苯基-2,2'：6'，2“-叔吡啶）是水和酸稳定的醛氢化催化剂环丁砜溶液中的羟基和酮在存在HOS（0）2CF3（三氟甲磺酸）作为脱水助催化剂的情况下，它们将1,2-己二醇直接转化为正己醇和己烷。 -吡啶吡啶配合物在温度为250°C的温度下以及在硫磺水溶液或纯水中都稳定且具活性，可以将甘油转化为正丙醇，最终以丙烷为最终反应产物，直至定量收率。是羰基物质[（4'-R-2,2'：6'，2“ -terpy）Ru（C0）（H20）21-（0TH，（R = H，Ph）醛（1,2,6-己醛-己二醇和3-羟基丙醛（甘油））在反应混合物中通过酸催化脱水生成。二聚体[{（4'-pheny1-2,2'：6'，2“ -terpy）Ru（C0）12（11-0CH，）21（0TH2）的结构已由单晶X-射线晶体学（空间群P1（a = 8.2532（17）; b = 12.858（3）; c = 14.363（3）A; a = 64.38（3）; / 3 = 77.26（3）; y = 87.12（3） °，R = 4.36％）。

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