Heterobimetallic Pd/Mn and Pd/Co complexes as efficient and stereoselective catalysts for sequential Cu-free Sonogashira coupling-alkyne semi-hydrogenation reactions.

A series of heterobimetallic PdII/MII complexes (MII = Mn, Co) were synthesised and tested as precatalysts for sequential Sonogashira coupling-alkyne semi-hydrogenation reactions to form Z-aryl alkenes. The carbometalated heterobimetallic PdII/CoII complex CoPdL3' demonstrated an apparent cooperative effect compared to the corresponding monometallic counterparts. This compound was identified as a potent single-molecule catalyst for the one-pot Cu-free Sonogashira coupling of aryl bromides with terminal alkynes followed by chemo- and stereoselective semi-hydrogenation of the alkyne intermediate using NH3·BH3 as a hydrogen source. Furthermore, different aromatic substrates have been tested to show the generality of the reaction for the synthesis of Z-alkenes, including biologically active combretastatin A-4. In addition, the homogeneous nature of the catalytically active species was demonstrated.