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Water‐Promoted Generation of a Diazairida Homobarrelene by CC Coupling Between an Iridacyclic Alkylidene and Acetonitrile
Author(s) -
Espada María F.,
LópezSerrano Joaquín,
Poveda Manuel L.,
Carmona Ernesto
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201503149
Subject(s) - chemistry , acetonitrile , isomerization , ligand (biochemistry) , cationic polymerization , medicinal chemistry , iridium , hydride , denticity , stereochemistry , methyl iodide , bicyclic molecule , molecule , polymer chemistry , crystallography , catalysis , organic chemistry , crystal structure , hydrogen , biochemistry , receptor
The stable cationic iridacyclopentenylidene [Tp Me2 Ir(CHC(Me)C(Me)C H 2 (NCMe)]PF 6 ( A ; Tp Me2 =hydrotris(3,5‐dimethylpyrazolyl)borate) has been obtained by α‐hydride abstraction from the iridacyclopent‐2‐ene [Tp Me2 Ir(CH 2 C(Me)C(Me)C H 2 )(NCMe)]. Complex A exhibits Brønsted–Lowry acidity at the IrCH 2 and proximal (relative to IrCH 2 ) 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 [Tp Me2 Ir(CHC(Me)C(Me)CH 2 )(NCMe) 2 ]PF 6 , which is capable to engage in a water‐promoted CC coupling with the MeCN co‐ligands. The product is an aesthetically appealing bicyclic structure that resembles the hydrocarbon barrelene.