Synthesis, reaction and catalysis of heterodinuclear organoplatinum or palladium complexes having M-M′ and M-C bonds without M-M′ connecting ligand

► Heterodinuclear organometallic complexes without connecting ligands are synthesized. ► Reversible σ-bound organic ligand transfer from M to M′ is shown. ► Enhanced CO insertion and selective C-S bond cleavage of thiiranes are presented. ► Heterodinuclear complexes catalyze carbonylation of thietane. ► Pd-catalyzed insertion of olefin or acetylene into Mo(or W)-H bond is described.