Journal
ORGANOMETALLICS
Volume 36, Issue 4, Pages 801-817Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.6b00864
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Funding
- Australian Research Council [FT130101713]
- UWA
- Australian Research Council [FT130101713] Funding Source: Australian Research Council
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While attempting to prepare a series of cationic NHC-Ir complexes of general formula [(NHC)Ir(COD)](+) via the silver salt metathesis reaction of its precursor (NHC)Ir(COD)Cl in dichloromethane, we unexpectedly synthesized [(mu-Cl){(2,7-SICyNap)Ir(COD))center dot{Ag(OTf)}], a chlotide-bridged Ir-Ag adduct. This result led us to investigate the chloride abstraction from the (NHC)Ir(COD)Cl systein in detail. We show how the outcome of this ubiquitous reaction is dependent on a fine balance between the nucleophilicity of the weakly coordinating anion (WCA) and the polarity/coordinating ability of the reaction medium. A frequently encountered alternative to using silver salts is also presented and compared. The experimental difference in the reactivitieS of cationic catalysts in a representative intramolecular hydroamination reaction shows how a cationic Ir-Ag adduct can fail to deliver the reaction product through what appears to be a stabilization of the catalytically inactive iridium-silver intermediate by the educt.
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