Use of [SbF6]鈭?/sup> to Isolate Cationic Copper and Silver Adducts with More than One Ethylene on the Metal Center

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• 作者：Mauro Fianchini ; Charles F. Campana ; Bhaskar Chilukuri ; Thomas R. Cundari ; Vaclav Petricek ; H. V. Rasika Dias
• 刊名：Organometallics
• 出版年：2013
• 出版时间：May 24, 2013
• 年：2013
• 卷：32
• 期：10
• 页码：3034-3041
• 全文大小：522K
• 年卷期：v.32,no.10(May 24, 2013)
• ISSN：1520-6041

文摘

A cationic tris(ethylene)copper(I) and tris(ethylene)silver(I) adduct has been isolated using hexafluoroantimonate counterion. X-ray crystallographic analysis shows that the metal atom in these adducts coordinates to three ethylene molecules in a trigonal planar fashion, forming a spoke-wheel arrangement. In [M(C₂H₄)₃][SbF₆] adducts (M = Cu, Ag, Au), the average M鈥揅 distances of 2.189 脜 for Cu and 2.410 脜 for Ag can be compared with the corresponding distance of 2.268 脜 for Au and show that the copper(I) complex has the shortest while the silver adduct displays the longest M鈥揅 distances. These agree well with the computed values (2.172, 2.408, and 2.308 脜 for Cu, Ag, and Au analogues, respectively) and follow the same trend as the covalent radii of M(I). Structural data on [渭₃-Cl{Cu(C₂H₄)₂}₃][SbF₆]₂, which features bis(ethylene)copper(I) moieties, are also presented. It has a trigonal planar Cu₃Cl core with a triply bridging chloride ion bonded to three trigonal planar copper centers. Ethylene molecules are bonded in an 畏²-fashion. The data indicate that while these [M(C₂H₄)₃]⁺ complexes may be primarily electrostatic in their metal鈥揺thylene binding, there remains an important covalent contribution, particularly for the copper and gold congeners.