Rock 鈥榥鈥?Roll With Gold: Synthesis, Structure, and Dynamics of a (bipyridine)AuCl3 Complex

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• 作者：Anthony P. Shaw ; Manik Kumer Ghosh ; Karl W. T枚rnroos ; David S. Wragg ; Mats Tilset ; Ole Swang ; Richard H. Heyn ; S酶ren Jakobsen
• 刊名：Organometallics
• 出版年：2012
• 出版时间：October 22, 2012
• 年：2012
• 卷：31
• 期：20
• 页码：7093-7100
• 全文大小：417K
• 年卷期：v.31,no.20(October 22, 2012)
• ISSN：1520-6041

文摘

Our previously reported microwave synthesis of (N鈥揘)AuClb>2b>⁺ complexes (where N鈥揘 = 2,2鈥?bipyridine (bpy) and sterically unencumbered bpy derivatives) was used to prepare derivatives where the bpy moiety was substituted in the 6,6鈥?positions. Instead of the square-planar complexes, these reactions produced neutral (N鈥揘)AuClb>3b> complexes. In these, the tethered N鈥揘 ligand is bonded such that one N occupies a regular position in the square coordination plane of the Au(III) center and the other N occupies a pseudoaxial position, interacting with Au through an elongated Au鈥揘 bond, as determined by X-ray crystallography of two complexes. Variable-temperature ¹H NMR spectroscopy reveals that the two sites of the N鈥揘 ligand undergo exchange on the NMR time scale. For N鈥揘 = 6,6鈥?Meb>2b>bpy the activation parameters were determined to be 螖H = 8.5 卤 0.4 kcal mol^鈥? and 螖S = 0.7 卤 2.0 cal K^鈥? mol^鈥?. The dynamic behavior of (6,6鈥?Meb>2b>bpy)AuClb>3b> was investigated by a DFT computational study, which detailed the in-plane rocking motion seen by NMR as well as decoordination of the axially bonded N with concomitant rolling of half of the bpy moiety by rotation around the central C鈥揅 bond of the bidentate ligand.