Silica-Supported Molybdenum Oxo Alkylidenes: Bridging the Gap between Internal and Terminal Olefin Metathesis.,Angewandte Chemie International Edition

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Silica-Supported Molybdenum Oxo Alkylidenes: Bridging the Gap between Internal and Terminal Olefin Metathesis.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-07-11 , DOI: 10.1002/anie.201903325
Margherita Pucino ₁ , Feng Zhai ₂ , Christopher P Gordon ₁ , Deni Mance ₁ , Amir H Hoveyda _{3,

4} , Richard R Schrock ₂ , Christophe Copéret ₁

Affiliation

Grafting a molybdenum oxo alkylidene on silica (partially dehydroxylated at 700 °C) affords the first example of a well‐defined silica‐supported Mo oxo alkylidene, which is an analogue of the putative active sites in heterogeneous Mo‐based metathesis catalysts. In contrast to its tungsten analogue, which shows poor activity towards terminal olefins because of the formation of a stable off‐cycle metallacyclobutane intermediate, the Mo catalyst shows high metathesis activity for both terminal and internal olefins that is consistent with the lower stability of Mo metallacyclobutane intermediates. This Mo oxo metathesis catalyst also outperforms its corresponding neutral silica‐supported Mo and W imido analogues.

中文翻译：

二氧化硅支持的氧化羰基钼炔金属：弥合内部和末端烯烃复分解之间的间隙。

在二氧化硅上接枝钼氧代亚烷基（在700°C时会部分脱羟基）提供了一个定义明确的二氧化硅负载的钼氧代亚烷基的第一个例子，它是多相Mo基复分解催化剂中假定的活性位点的类似物。与其钨类似物相比，钨类似物由于形成稳定的循环外金属环丁烷中间体而对末端烯烃的活性差，而钼催化剂对末端和内烯烃均显示出高复分解活性，这与钼金属环丁烷的较低稳定性相符。中间体。这种Mo oxo复分解催化剂的性能也优于其相应的中性二氧化硅负载的Mo和W亚氨基类似物。

更新日期：2019-07-11

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