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Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes

机译:高氧化态亚氨基杂原子取代的亚炔基配合物的合成

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摘要

Reactions between Mo(NAr)(CHR)(Me2Pyr)-(OTPP) (Ar = 2,6-i-Pr2C6H3, R = H or CHCMe2Ph, Me2Pyr = 2,5-dimethylpyrrolide, OTPP = O-2,3,5,6-Ph4C6H) and CH2=CHX where X = B(pin), SiMe3, N-carbazolyl, N-pyrrolidinonyl, PPh2, OPr, or SPh lead to Mo(NAr)(CHX)-(Me2Pyr)(OTPP) complexes in good yield. All have been characterized through X-ray studies (as an acetonitrile adduct in the case of X = PPh2). The efficiencies of metathesis reactions initiated by Mo(NAr)(CHX)(Me2Pyr)(OTPP) complexes can be rationalized on the basis of steric factors; electronic differences imposed as a consequence of X being bound to the alkylidene carbon do not seem to play a major role. Side reactions that promote catalyst decomposition do not appear to be a serious limitation for Mo=CHX species.
机译:Mo(NAr)(CHR)(Me2Pyr)-(OTPP)之间的反应(Ar = 2,6-i-Pr2C6H3,R = H或CHCMe2Ph,Me2Pyr = 2,5-二甲基吡咯化物,OTPP = O-2,3,5 ,6-Ph4C6H)和CH2 = CHX其中X = B(pin),SiMe3,N-咔唑基,N-吡咯烷基,PPh2,OPr或SPh生成Mo(NAr)(CHX)-(Me2Pyr)(OTPP)络合物产量高。所有化合物均已通过X射线研究(在X = PPh2情况下为乙腈加合物)进行了表征。 Mo(NAr)(CHX)(Me2Pyr)(OTPP)配合物引发的复分解反应的效率可以根据空间因素进行合理化;由于X与亚烷基碳键合而产生的电子差异似乎没有主要作用。促进催化剂分解的副反应似乎对Mo = CHX物种没有严重的限制。

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