Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes

The catalytic activity of a set of mono- and bimetallic Rh( i ) and Ir( i ) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkynes. The hydrothiolation of 1-hexyne with t...

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Bibliographic Details
Published in:Catalysis science & technology 2021-02, Vol.11 (2), p.516-523
Main Authors: Tolley, Lewis C, Fernández, Israel, Bezuidenhout, Daniela I, Guisado-Barrios, Gregorio
Format: Article
Language:English
Subjects:
Additives
Alkynes
Aromatic compounds
Bimetals
Catalysts
Catalytic activity
Catalytic converters
Chelation
Displays
Iridium compounds
Mathematical analysis
Reaction mechanisms
Rhodium
Selectivity
Thiols
Thiophenol
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Summary:The catalytic activity of a set of mono- and bimetallic Rh( i ) and Ir( i ) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkynes. The hydrothiolation of 1-hexyne with thiophenol in the absence of an external base or other additives was selected as a model reaction. All rhodium complexes are highly selective catalysts towards Markovnikov product formation and display superior activity compared to the related iridium derivatives. DFT calculations were carried out to rationalize the reaction mechanism and selectivity of this process. Neutral dinuclear [Rh 2 Cl 2 (cod) 2 (μ- COC )] was found to be the most effective catalyst for this transformation. Its applicability was further studied towards the hydrothiolation of different alkyl and aryl alkynes using predominantly aryl thiols and proved to be one of the most active and selective catalysts towards the α-vinyl sulfide product to date. The performance of a set of mono- and bimetallic Rh( i ) and Ir( i ) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkynes.
ISSN:2044-4753
2044-4761
DOI:10.1039/d0cy01647k