An air-stable rhodium(I)-oxygen adduct featuring a CNC-pincer
ligand, based on 1,2,3-triazol-5-ylidenes, catalyzes the homodimerization
and hydrothiolation of alkynes, affording the gemenyne
and α-vinyl sulfide isomers, respectively, with excellent
selectivity. A one-pot stepwise strategy allows the selective
catalytic preparation of non-symmetric bis-vinyl sulfides, as well
as the alkyne dimerization-hydrothiolation tandem reaction.