Crystal Structure and Computational Investigation of an Analogue of Grubbs鈥?Second Generation Catalyst with a Fluorous Phosphine

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• 作者：Robert Tuba ; Edward N. Brothers ; Joseph H. Reibenspies ; Hassan S. Bazzi ; John A. Gladysz
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：September 17, 2012
• 年：2012
• 卷：51
• 期：18
• 页码：9943-9949
• 全文大小：446K
• 年卷期：v.51,no.18(September 17, 2012)
• ISSN：1520-510X

文摘

A fluorous phosphine analogue of Grubbs鈥?second generation olefin metathesis catalyst, (H₂IMes)((R_f8(CH₂)₂)₃P)(Cl)₂Ru(=CHPh) (1; H₂IMes/R_f8 = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene/(CF₂)₇CF₃) is crystallized and the X-ray structure analyzed in detail. The bond lengths and angles about ruthenium are compared to those of two solvates and five derivatives of Grubbs鈥?second generation catalyst. All exhibit distorted square pyramidal geometries in which the alkylidene ligands occupy apical positions, and geometric trends are interpreted with the help of density functional calculations. The perfluoroalkyl groups (1) exhibit helical conformations, as manifested by various torsional relationships, (2) segregate in the lattice, and (3) align in pairs of opposite helical chiralities.