期刊
ORGANOMETALLICS
卷 36, 期 11, 页码 2198-2207出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.7b00251
关键词
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资金
- Spanish Ministerio de Economia y Competitividad (MINECO/FEDER) [CTQ2013-42532-P, CTQ2016-75884-P]
- Diputacion General de Aragon [E07]
- CONSOLIDER INGENIO [CSD2009-00050]
- Spanish Ministerio de Economia y Competitividad (MINECO) [IJCI-2015-27029]
New Rh-I-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 alpha-vinyl sulfides. Reactivity studies and DFT calculations have revealed a new nonoxidative catalytic pathway, passing through Rh-I 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 Rh-I active species, whereas the pi-acceptor character of the carbonyl ligand hinders the oxidative addition process. In addition, the stereochemistry of the key thiolate-pi-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.
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