Molybdenum Monoaryloxide Pyrrolide Alkylidene Complexes That Contain Mono-ortho-substituted Phenyl Imido Ligands

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• 作者：Alejandro G. Lichtscheidl ; Victor W. L. Ng ; Peter M眉ller ; Michael K. Takase ; Richard R. Schrock
• 刊名：Organometallics
• 出版年：2012
• 出版时间：March 26, 2012
• 年：2012
• 卷：31
• 期：6
• 页码：2388-2394
• 全文大小：425K
• 年卷期：v.31,no.6(March 26, 2012)
• ISSN：1520-6041

文摘

Monaryloxide pyrrolide (MAP) molybdenum imido alkylidene complexes of the type Mo(NAr^X)(CHCMe₂R)(Me₂Pyr)(OR鈥? (Me₂Pyr = 2,5-dimethylpyrrolide) have been prepared in which NAr^X is an ortho-substituted phenylimido group (X = Cl (NAr^Cl), CF₃ (NAr^CF3), i-Pr (NAr^iPr), t-Bu (NAr^tBu), mesityl (NAr^M), or TRIP (TRIP = triisopropylphenyl; NAr^T)) and OR鈥?= O-2,3,5,6-(C₆H₅)₄C₆H (OTPP), O-2,6-(2,4,6-Me₃C₆H₂)₂C₆H₃ (OHMT), or O-2,6-(2,4,6-i-Pr₃C₆H₂)₂C₆H₃ (OHIPT). The object was to explore to what extent relatively 鈥渓arge鈥?NAr^M or NAr^T ligands would alter the performance of MAP catalysts in reactions that have been proposed to depend upon the relative size of the imido and OR鈥?groups. Preliminary studies employing the ring-opening metathesis polymerization of 5,6-dicarbomethoxynorbornadiene as a measure of selectivity suggest that a single phenylimido ortho substituent, even in an NAr^M or NAr^T group, does not produce any unique behavior and that the outcome of the ROMP reaction correlates with the overall relative size of the imido and OR鈥?group. Single-crystal X-ray structures of six species that contain the new NAr^M or NAr^T groups are reported.