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Stabilization of eta(3)-indenyl compounds by sterically demanding N,N-chelating ligands in the molybdenum coordination sphere

机译:钼配位空间中的空间需求性N,N-螯合配体稳定eta(3)-茚基化合物

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摘要

A series of eta(3)-indenyl molybdenum compounds [(eta(3)-4,7-Me2C9H5)Mo(CO)(2)(L-N,L-N)Cl] (L-N,L-N = bpy, phen, pyma), isostructural with well-known eta(3)-allyl compounds, was synthesized from the recently established halide synthon [{(eta(5)-4,7-Me2C9H5)Mo(CO)(2)(mu-Cl)}(2)]. The low stability of the hexacoordinated h 3-indenyl molybdenum species in solution has been overcome by a modification of the chelating ligand. Hence, the dissociation of the compounds bearing ligands with methyl groups beside nitrogen donor atoms (e.g. 6,6'-Me-2-bpy, 2,9-Me-2-phen; 2,9-Me-2-4,7-Ph-2-phen) is strongly disfavored due to the steric requirements of the substituents. The considerable discrimination of the pentacoordinated species enables the use of [(eta(5)-4,7-Me2C9H5)Mo(CO)(2)(2,9-Me-2-phen)][BF4] for the assembly of derivatives bearing other halides and pseudohalides in the coordination sphere of molybdenum. The current study further describes some other new indenyl complexes accessible from [{(eta(5)-4,7-Me2C9H5)Mo(CO)(2)(mu-Cl)}(2)]. All structural types presented in this experimental study were supported by X-ray crystallographic data.
机译:一系列eta(3)-茚基钼化合物[(eta(3)-4,7-Me2C9H5)Mo(CO)(2)(LN,LN)Cl](LN,LN = bpy,phen,pyma),从最近建立的卤化物合成子[{(eta(5)-4,7-Me2C9H5)Mo(CO)(2)(mu-Cl)}(2 )]。六配位的h 3-茚基钼物质在溶液中的低稳定性已通过螯合配体的修饰得以克服。因此,带有配体的化合物与除氮供体原子外的甲基一起解离(例如6,6'-Me-2-bpy,2,9-Me-2-phen,2,9-Me-2-4,7 -Ph-2-phen)由于取代基的空间要求而被强烈反对。对五配位物种的显着区分使得可以使用[[eta(5)-4,7-Me2C9H5)Mo(CO)(2)(2,9-Me-2-phen)] [BF4]的组装在钼配位区内带有其他卤化物和假卤化物的衍生物。当前的研究进一步描述了可从[{(eta(5)-4,7-Me2C9H5)Mo(CO)(2)(mu-Cl)}(2)获得的一些其他新型茚基配合物。本实验研究中提出的所有结构类型均得到X射线晶体学数据的支持。

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