Grafting mechanism and olefin metathesis activity of well-defined silica-supported Mo imido alkyl alkylidene complexes
Grafting mechanism and olefin metathesis activity of well-defined silica-supported Mo imido alkyl alkylidene complexes
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DOI：
10.1016/j.crci.2007.02.017
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发表时间：
2008-01-01
影响因子：
1.6
通讯作者：
Schrock, Richard R.
中科院分区：
文献类型：
--
作者：
Blanc, Frederic;Salameh, Alain;Schrock, Richard R.
将[Mo(NaR)(=CHCMe2R)(CH(2)t(3)Bu)(2)]，1-R(R=Me或Ph)接枝到SiO_2-(700)表面，通过标记(胶体和固体核磁共振)和反应性研究(监测引发)，通过Mo-C sigma键的亲电断裂得到2-R。类似地，分子硅醇衍生物也与1-Ph反应，直接得到单硅氧基衍生物。因此，表面或分子硅烷醇具有与pKa和gt=9的醇和酚类似的反应活性。最后，表面络合物2-R(R=Me或Ph)是一种高效的烯烃歧化催化剂。
Grafting of [Mo(NAr)(=CHCMe2R)(CH(2)t(3)Bu)(2)], 1-R (R = Me or Ph) on the surface silanols of SiO2-(700) gives 2-R through the electrophilic cleavage of the Mo-C sigma-bond according to labelling (GUMS and solid-state NMR) and reactivity studies (monitoring initiation). Similarly, molecular silanol derivatives react with 1-Ph also to give directly the monosiloxy derivatives. Therefore, surface or molecular silanols have reactivities similar to alcohols and phenols having pKa >= 9. Finally, the surface complex 2-R (R = Me or Ph) is a highly efficient olefin metathesis catalyst.