Affiliation:
1. Institute of Inorganic Chemistry Christian-Albrechts-University of Kiel Max-Eyth Straße 2 24118 Kiel Germany
2. Institute of Physical Chemistry Christian-Albrechts-University of Kiel Max-Eyth Straße 1 24118 Kiel Germany
Abstract
AbstractThe conversion of an azacalixpyridine‐supported Mo(0) tricarbonyl into a Mo(VI) trioxo complex with dioxygen (O2) 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.