Unusual Phosphorus−Phosphorus Double Bond Contraction upon Mono- and Di-auration of a Diphosphene

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• 作者：David V. Partyka ; Marlena P. Washington ; Thomas G. Gray ; James B. Updegraff III ; John F. Turner ; II ; John D. Protasiewicz
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：July 29, 2009
• 年：2009
• 卷：131
• 期：29
• 页码：10041-10048
• 全文大小：323K
• 年卷期：v.131,no.29(July 29, 2009)
• ISSN：1520-5126

文摘

The diphosphene Mes*P═Mes* (Mes* = 2,4,6-tri-tert-butylphenyl; 1) reacted with 1 or 2 equiv of Au(tht)Cl (tht = tetrahydrothiophene) to produce the stable monoaurated adduct Mes*{AuCl}P═PMes* (2) or diaurated adduct Mes*{AuCl}P═P{AuCl}Mes* (3) respectively. The products were characterized by X-ray crystallography, UV−visible, IR, Raman, and multinuclear NMR spectroscopies, as well as by density functional theory calculations. The crystallographic and Raman spectroscopic data provide physical evidence that the P═P bond grows shorter and increases in strength upon auration; these observations are further examined by DFT calculations for a series of model compounds CH₃{AuCl}_nP═P{AuCl}_n′CH₃ 1′−3′ (n, n′ = 0 or 1). Compounds 1−3 represent a rare series of crystallographically characterized diphosphenes bearing zero, one, or two AuCl units on each phosphorus atom, allowing for a systematic analysis of the impact of Lewis acids on the phosphorus−phosphorus double bond.