Related Experiment Video
Updated: Jun 16, 2025

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Ambiphilic Reactivity of Iridium Complexes with N-Heterocyclic Vinylidene Ligands
Tak Hin Wong1, Paul Varava1, Farzaneh Fadaei-Tirani1
1Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Abstract:
Room-temperature stable diazoolefins provide access to a unique class of carbon-donor ligands: N-heterocyclic vinylidenes. Herein, we describe iridium complexes with terminal N-heterocyclic vinylidene ligands. Cationic complexes of type [Cp*IrClL]X (X = SbF6, OTf; L = N-heterocyclic vinylidene) were obtained by reaction of (Cp*IrCl2)2 with an N-heterocyclic diazoolefin, followed by chloride abstraction. Reduction instead of chloride abstraction gave a neutral Cp*IrL complex with a "pogo stick" geometry. Crystallographic analyses of the complexes revealed very short iridium-carbon bonds, suggesting partial carbyne character. The vinylidene ligands display ambiphilic reactivity. The cationic complex forms covalent adducts with halides and pseudohalides, whereas the neutral complex reacts with electrophiles. These transformations generate rare carbon-donor species, including anionic N-heterocyclic olefins with pronounced carbene character or a side-on bound alkylidene ketene.
More Related Videos
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Related Concept Videos
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Radical Reactivity: Intramolecular vs Intermolecular
Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Radical Reactivity: Nucleophilic Radicals