Thiolate-bridged dirhodium and diiridium complexes can facilely realize heterolytic cleavage of H2 across the metal–sulfur bond to generate the corresponding hydride bridged complexes. Furthermore, terminal alkynes can insert the Rh–H–Rh fragment to afford σ:π alkenyl bridged complexes and then convert to the corresponding alkenes in the presence of a reductant and an acid.
