Syntheses and Structures of Molybdenum Imido Alkylidene Pyrrolide and Indolide Complexes
Syntheses and Structures of Molybdenum Imido Alkylidene Pyrrolide and Indolide Complexes
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钼亚氨基亚烷基吡咯和吲哚配合物的合成和结构
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发表时间：
2008
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通讯作者：
P. Müller
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作者：
S. Marinescu;Rojendra Singh;Adam S. Hock;K. M. Wampler;R. Schrock;P. Müller
Mo(NAd)(CHCMe2Ph)(2,5-Me2NC4H2)2 (1; Ad = 1-金刚烷基)的 X 射线结构研究表明它含有一个 η1-2,5-Me2NC4H2 环和一个 η5-2,5-Me2NC4H2 环。含有 2,3,4,5-四甲基吡咯烷、2,5-二异丙基吡咯烷或 2,5-二苯基吡咯烷的 Mo(NAr)(CCHCMe2Ph)(吡咯烷)2 (Ar = 2,6-i-Pr2C6H3) 配合物的结构与 1 类似。相反，Mo(NAr)(CH2CMe2Ph)(indolide)2 (6) 被证明含有两个 η1-结合吲哚内酯。单六氟叔丁醇吡咯酯(MAP)物质可以通过将一当量的Me(CF 3 ) 2 COH添加到双吡咯烷中或通过吡咯锂和双六氟叔丁醇之间的反应来制备。双吡咯烷的三甲基膦加合物 Mo(NAd)(CHCMe2Ph)(η1-NC4H4)2(PMe3) 已被制备并进行了结构表征，而 MAP 六氟叔丁醇物质的 PMe3 加合物被发现具有大约反式与吡咯烷烃结合的 PMe3。该加合物可作为烯烃中初始烯烃加合物结构的模型......
An X-ray structural study of Mo(NAd)(CHCMe2Ph)(2,5-Me2NC4H2)2 (1; Ad = 1-adamantyl) reveals it to contain one η1-2,5-Me2NC4H2 ring and one η5-2,5-Me2NC4H2 ring. The structures of Mo(NAr)(CHCMe2Ph)(pyrrolide)2 (Ar = 2,6-i-Pr2C6H3) complexes that contain 2,3,4,5-tetramethylpyrrolides, 2,5-diisopropylpyrrolides, or 2,5-diphenylpyrrolides are analogous to that of 1. In contrast, Mo(NAr)(CH2CMe2Ph)(indolide)2 (6) was shown to contain two η1-bound indolides. Monohexafluoro-t-butoxide pyrrolide (MAP) species can be prepared, either through addition of one equiv of Me(CF3)2COH to a bispyrrolide or through reactions between the lithium pyrrolide and the bishexafluoro-t-butoxide. A trimethylphosphine adduct of a bispyrrolide, Mo(NAd)(CHCMe2Ph)(η1-NC4H4)2(PMe3), has been prepared and structurally characterized, while a PMe3 adduct of MAP hexafluoro-t-butoxide species was found to have PMe3 bound approximately trans to the pyrrolide. This adduct serves as a model for the structure of the initial olefin adduct in olef...