Water‐Promoted Generation of a Diazairida Homobarrelene by CC Coupling Between an Iridacyclic Alkylidene and Acetonitrile |
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| Authors: | María F. Espada Prof. Dr. Manuel L. Poveda Prof. Dr. Ernesto Carmona |
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| Affiliation: | Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO‐CINQA), Consejo Superior de Investigaciones Científicas (CSIC) and Universidad de Sevilla, Avda. Américo Vespucio, 49, 41092 Sevilla (Spain) |
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| Abstract: | The stable cationic iridacyclopentenylidene [TpMe2Ir(?CHC(Me)?C(Me)C H2(NCMe)]PF6 ( A ; TpMe2=hydrotris(3,5‐dimethylpyrazolyl)borate) has been obtained by α‐hydride abstraction from the iridacyclopent‐2‐ene [TpMe2Ir(CH2C(Me)?C(Me)C H2)(NCMe)]. Complex A exhibits Brønsted–Lowry acidity at the Ir? CH2 and proximal (relative to Ir? CH2) methyl sites. The coordination of an extra molecule of acetonitrile to the iridium center initiates the reversible isomerization of the chelating carbon chain of A to the monodentate butadienyl ligand of complex [TpMe2Ir(CH?C(Me)C(Me)?CH2)(NCMe)2]PF6, which is capable to engage in a water‐promoted C? C coupling with the MeCN co‐ligands. The product is an aesthetically appealing bicyclic structure that resembles the hydrocarbon barrelene. |
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| Keywords: | alkylidenes C C coupling iridium water catalysis |
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