Classical versus Bridged Allyl Ligands in Magnesium Complexes: The Role of Solvent

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• 作者：Stephen C. Chmely ; Christin N. Carlson ; Timothy P. Hanusa ; Arnold L. Rheingold
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：May 13, 2009
• 年：2009
• 卷：131
• 期：18
• 页码：6344-6345
• 全文大小：150K
• 年卷期：v.131,no.18(May 13, 2009)
• ISSN：1520-5126

文摘

Magnesium allyl complexes are regularly isolated with classical, σ-bonded ligands, and this has been thought to be their preferred mode of bonding. Density funtional theory calculations confirm that such bonding is the most stable mode when coordinated bases are present, but in their absence, π-bonded forms are expected to be lower in energy. The isolation of the unsolvated [Mg{C₃(SiMe₃)₂H₃}₂]₂ complex supports this prediction, as it is a dinuclear species in which two allyl ligands bridge the metals and display cation−π interactions with them.