Molybdenum(0)‐Tricarbonyl Complex Supported by an Azacalix‐pyridine Ligand: Synthesis, Characterization, Surface Deposition and Conversion to a Molybdenum(VI)‐Trioxo Complex with O2.

Adsorption of metal‐organic complexes on metallic surfaces to produce well‐defined single site catalysts is a novel approach combining the advantages of homogeneous and heterogeneous catalysis. To avoid the "surface trans‐effect" a dome‐shaped molybdenum(0) tricarbonyl complex supported by an tolylazacalix[3](2,6)pyridine ligand is synthesized. This vacuum‐evaporable complex both activates CO and reacts with molecular oxygen (O2) to form a Mo(VI) trioxo complex which in turn is capable of catalytically mediating oxygen transfer. The molybdenum tricarbonyl‐ and trioxo complexes are investigated in the solid state, in homogeneous solution and on noble metal surfaces (Cu, Au) employing a range of spectroscopic and analytical methods. [ABSTRACT FROM AUTHOR]