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Hydroxo-rhodium-N-heterocyclic carbene complexes as efficient catalyst precursors for alkyne hydrothiolation

AuthorsPalacios, Laura CSIC; Artigas, María José CSIC; Polo, Víctor; Lahoz, Fernando J. CSIC ORCID; Castarlenas, Ricardo CSIC ORCID; Pérez-Torrente, Jesús J. CSIC ORCID; Oro, Luis A. CSIC ORCID
Homogeneous catalysis
N-heterocyclic carbene
DFT calculations
Issue Date2013
PublisherAmerican Chemical Society
CitationACS Catalysis 3(12): 2910-2919 (2013)
AbstractThe new Rh-hydroxo dinuclear complexes stabilized by an N-heterocyclic carbene (NHC) ligand of type [Rh(μ-OH)(NHC)(η2-olefin)] 2 (coe, IPr (3), IMes (4); ethylene, IPr (5)) are efficient catalyst precursors for alkyne hydrothiolation under mild conditions, presenting high selectivity toward α-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 RhI-thiolato species Rh(SCH2Ph)(IPr)(η2-coe)(py) (6) and Rh(SCH 2Ph)(IPr)(η2-HCî - CCH2Ph)(py) (7), and the RhIII-hydride-dithiolato derivative RhH(SCH 2Ph)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. © 2013 American Chemical Society.
Publisher version (URL)http://dx.doi.org/10.1021/cs400739y
Identifiersdoi: 10.1021/cs400739y
e-issn: 2155-5435
Appears in Collections:(ISQCH) Artículos
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