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Design of highly selective alkyne hydrothiolation RhI-NHC catalysts: Carbonyl-triggered nonoxidative mechanism

AuthorsPalacios, Laura ; Meheut, Yoann; Galiana-Cameo, María; Artigas, María José ; Giuseppe, Andrea di ; Lahoz, Fernando J. ; Polo, Víctor; Castarlenas, Ricardo ; Pérez-Torrente, Jesús J. ; Oro, Luis A.
Issue Date2017
PublisherAmerican Chemical Society
CitationOrganometallics 36(11): 2198-2207 (2017)
AbstractNew RhI-IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-carbene) complexes bearing an N,O-pyridine-2-methanolato (N-O) bidentate ligand have been prepared. The carbonyl complex Rh(N-O)(IPr)(CO) efficiently catalyzes the hydrothiolation of a range of alkynes with high selectivity to α-vinyl sulfides. Reactivity studies and DFT calculations have revealed a new nonoxidative catalytic pathway, passing through RhI catalytic intermediates, which is driven by the interplay between the pyridine-2-methanolato and carbonyl ligands. The basic alkoxo ligand promotes the deprotonation of the thiol to generate the RhI active species, whereas the π-acceptor character of the carbonyl ligand hinders the oxidative addition process. In addition, the stereochemistry of the key thiolate-π-alkyne intermediate, which is determined by the electronic preference of the carbonyl ligand to coordinate cis to IPr, facilitates the rate-limiting alkyne thiometalation step.
Publisher version (URL)https://doi.org/10.1021/acs.organomet.7b00251
Identifiersdoi: 10.1021/acs.organomet.7b00251
issn: 0276-7333
e-issn: 1520-6041
Appears in Collections:(ISQCH) Artículos
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