[((CH3)5C5)Ir(η(4)-C6H6O)] | 93582-36-6

• 英文名称: [((CH3)5C5)Ir(η(4)-C6H6O)]
• CAS: 93582-36-6；219773-16-7
• 化学式: C₁₆H₂₁IrO
• 分子量: 421.562
• InChiKey: ULOFLLVOJPUHCS-UHFFFAOYSA-N

计算性质

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反应信息

• 作为产物：
  描述：

  [(η(5)-C5Me5)Ir(η(5)-C6H5O)][BF4] 、 sodium cyanoborohydride 以 乙腈 为溶剂， 以60%的产率得到[((CH3)5C5)Ir(η(4)-C6H6O)]
  参考文献：
  名称：

  Ir-Mediated Nucleophilic Ortho-Functionalization of Phenols:  Syntheses, Structures, Scope, and Limitation

  摘要：

  Treatment of [Cp*Ir(eta(5)-PhO)][BF4] (1) with hydride, deuteride, and C-, N-, and S-centered nucleophiles affords the stable eta(4)-phenol tautomers of the type [Cp*Ir(eta(4)-exo-2-(Nu)-C6H5O)] (2-6) {Nu = nucleophile}. In all cases regiospecific nucleophilic addition occurs at the ortho-position relative to C=O with exo-stereochemistry. The X-ray molecular structure of the first neutral phenol tautomer [Cp*Ir(eta(4)-exo-2-(CH(COMe)(2))-C6H5O] (4) was determined and provides valuable crystallographic information for an organic phenol tautomer. Oxidation of the novel dienone iridium complexes [Cp*Ir(eta(4)-exo-2-(Nu)-C6H5O)] by iodine provided a different type of products depending dramatically on the nature and electron properties of the 2-exo-nucleophile. For instance R3C-, RO-, and R3P-centered nucleophiles gave the related ortho-functionalized phenols along with the starting material recycled in the form of [Cp*Ir(mu-I)I](2). In dramatic contrast N- and S-centered nucleophiles showed a retronucleophilic addition or C-Nu bond cleavage as demonstrated by complexes 5 and 6 to give the starting material identified spectroscopically and by X-ray structure as [Cp*Ir(eta(5)-PhO)][I] (8). In the latter, a rationale involving a one-electron oxidation process is proposed to explain the experimental results.

  DOI：

  10.1021/om980828i