期刊
ACS CATALYSIS
卷 3, 期 12, 页码 2910-2919出版社
AMER CHEMICAL SOC
DOI: 10.1021/cs400739y
关键词
homogeneous catalysis; N-heterocyclic carbene; rhodium; hydroxides; hydrothiolation; DFT calculations
资金
- Spanish Ministerio de Economia y Competitividad (MEC/FEDER) of Spain [CTQ2010-15221, CTQ2012-3566S]
- Diputacion General de Aragon
- European Social Fund [E07]
- ARAID Foundation
- CONSOLIDER INGENIO under the Project MULTICAT [CSD2009-00050]
The new Rh-hydroxo dinuclear complexes stabilized by an N-heterocyclic carbene (NHC) ligand of type [Rh(mu-OH)(NHC)(eta(2)-olefin)](2) (coe, IPr (3), IMes (4); ethylene, IPr (5)) are efficient catalyst precursors for alkyne hydrothiolation under mild conditions, presenting high selectivity toward alpha-vinyl sulfides for a varied set of substrates, which is enhanced by pyridine addition. The structure of complex 3 has been determined by X-ray diffraction analysis. Several intermediates relevant for the catalytic process have been identified, including Rh-I-thiolato species Rh(SCH2Ph)(IPr)(eta(2)-coe)(py) (6) and Rh(SCH2Ph)(IPr)(eta(2)-HC CCH2Ph)(py) (7), and the Rh-III-hydride-dithiolato derivative RhH(SCH2Ph)(2)(IPr)(py) (8) as the catalytically active species. Computational DFT studies reveal an operational mechanism consisting of sequential thiol deprotonation by the hydroxo ligand, subsequent S-H oxidative addition, alkyne insertion, and reductive elimination. The insertion step is rate-limiting with a 1,2 thiometalation of the alkyne as the more favorable pathway in accordance with the observed Markovnikov-type selectivity.
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