title: Synthesis of iridium pyridinyl N-heterocyclic carbene complexes and their catalytic activities on reduction of nitroarenes.
abstract: Coordination of iridium(I) metal ions with a pyridinyl imidazol-2-ylidene ligand (pyNwedgeC-R) [R=Me, mesityl(2,4,6-trimethylphenyl)] that processes bulky substituents has been investigated. The iridium carbene complexes [(C-pyNwedgeC-R)IrCl(COD)] (COD=1,5-cyclooctadiene) are prepared via transmetalation from the corresponding silver carbene complexes. Upon the abstraction of chloride, the chelation of pyNwedgeC becomes feasible, resulting in the formation of [C,N-(pyNwedgeC-R)Ir(COD)](BF4) (4). The coordinated COD of complex 4 can be replaced by carbon monoxide to yield the corresponding carbonyl species [C,N-(pyNwedgeC-R)Ir(CO)2](BF4). The labile nature of the pyridinyl nitrogen donor is readily replaced by acetonitrile, as is evidenced by the NMR study. All iridium complexes show catalytic activity on the hydrogen-transfer reduction of carbonyl and nitro functionalities. By manipulation of the reaction conditions, the iridium-catalyzed reduction of nitroarenes can selectively provide aniline or azo compounds as the desired product.
authors.affiliation: Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.
authors.forename: Chao-Yu
authors.initials: CY
authors.lastname: Wang
authors.forename: Ching-Feng
authors.initials: CF
authors.lastname: Fu
authors.forename: Yi-Hong
authors.initials: YH
authors.lastname: Liu
authors.forename: Shei-Ming
authors.initials: SM
authors.lastname: Peng
authors.forename: Shiuh-Tzung
authors.initials: ST
authors.lastname: Liu