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Title: | Design of highly selective alkyne hydrothiolation RhI-NHC catalysts: Carbonyl-triggered nonoxidative mechanism |
Authors: | Palacios, Laura ![]() ![]() ![]() ![]() ![]() ![]() ![]() |
Issue Date: | 2017 |
Publisher: | American Chemical Society |
Citation: | Organometallics 36(11): 2198-2207 (2017) |
Abstract: | New 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 |
URI: | http://hdl.handle.net/10261/177130 |
DOI: | 10.1021/acs.organomet.7b00251 |
Identifiers: | doi: 10.1021/acs.organomet.7b00251 issn: 0276-7333 e-issn: 1520-6041 |
Appears in Collections: | (ISQCH) Artículos |
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