Oxidative Decarbonylation of an Azacalixpyridine-Supported Mo(0)-Tricarbonyl to a Mo(VI)-Trioxo Complex with Dioxygen in Solution and on Au(111): Determination of Molecular Mechanism.

The conversion of an azacalixpyridine-supported Mo(0) tricarbonyl into a Mo(VI) trioxo complex with dioxygen (O 2 ) is investigated in homogeneous solution and in a molecular film adsorbed on Au(111) using a variety of spectroscopic and analytical methods. These studies in particular show that the dome-shaped carbonyl complex adsorbed on the metal surface has the ability to bind and activate gaseous oxygen, overcoming the so-called surface trans-effect. Furthermore, the rate of the conversion dramatically increases by irradiation with light. This observation is explained with the help of complementary DFT calculations and attributed to two different pathways, a thermal and a photochemical one. Based on the experimental and theoretical findings, a molecular mechanism for the conversion of the carbonyl to the oxo complex is derived.