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

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.Financial support from the Spanish Ministerio de Economía y Competitividad (MINECO/FEDER) under the Projects CTQ2013-42532-P and CTQ2016-75884-P, the Diputación General de Aragón (E07) and CONSOLIDER INGENIO-2010, under the Project MULTICAT (CSD2009-00050) are gratefully acknowledged. A.D.G. thanks the Spanish Ministerio de Economia y Competitividad (MINECO) for the post- doctoral grant Juan de la Cierva - Incorporacion 2015 (IJCI-2015-27029).Peer Reviewe