Design of Highly Selective Alkyne Hydrothiolation Rh^I‑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.