Abstract
Treatment of [Cp*Ir(η5-PhO)][BF4] (1) with hydride, deuteride, and C-, N-, and S-centered nucleophiles affords the stable η4-phenol tautomers of the type [Cp*Ir(η4-exo-2-(Nu)-C6H5O)] (2−6) {Nu = nucleophile}. In all cases regiospecific nucleophilic addition occurs at the ortho-position relative to CO with exo-stereochemistry. The X-ray molecular structure of the first neutral phenol tautomer [Cp*Ir(η4-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(η4-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(μ-I)I]2. In dramatic contrast N- and S-centered nucleophiles showed a retronucleophilic addition or C−Nu bond c...
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