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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Ansa-bridged eta(5)-cyclopentadienyl molybdenum and tungsten complexes: synthesis, structure and application in olefin epoxidation
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Ansa-bridged eta(5)-cyclopentadienyl molybdenum and tungsten complexes: synthesis, structure and application in olefin epoxidation

机译:Ansa桥联的eta(5)-环戊二烯基钼和钨配合物:烯烃环氧化的合成,结构和应用

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摘要

Ansa-bridged eta(5)-cyclopentadienyl molybdenum and tungsten tricarbonyl complexes of formula [M(eta(5)-C5H4(CH2)(3)-eta(1)-CH2)(CO)(3)] (M= Mo or W) were synthesized and the X-ray crystal structure of the tungsten complex is reported. In the epoxidation of cyclooctene the molybdenum compound shows a high catalytic activity, approaching the observed activities for the most reactive unbridged complexes of composition CpMo(CO)(3)X (X=Cl, CH3). The activity of the tungsten complex is also amongst the highest catalytic activities for the olefinic epoxidation of complexes with the composition CpW(CO)(3)X and WO2X2L2, reported so far. The low ring strain of the ansa-bridged system improves the stability of the complexes under oxidative conditions considerably in comparison to derivatives with a shorter bridge and therefore paves the way to introduction of chirality in these systems.
机译:式[M(eta(5)-C5H4(CH2)(3)-eta(1)-CH2)(CO)(3)的Ansa桥联的eta(5)-环戊二烯基钼和钨三羰基钨配合物或W)被合成并且报道了钨配合物的X射线晶体结构。在环辛烯的环氧化中,钼化合物显示出高催化活性,接近组成CpMo(CO)(3)X(X = Cl,CH3)的最具反应性的未桥联络合物的活性。到目前为止,钨配合物的活性也是配合物CpW(CO)(3)X和WO2X2L2的配合物烯属环氧化的最高催化活性之一。与具有较短桥的衍生物相比,ansa-桥联系统的低环应变大大提高了配合物在氧化条件下的稳定性,因此为在这些系统中引入手性铺平了道路。

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