Zero‐Valent Amino‐Olefin Cobalt Complexes as Catalysts for Oxygen Atom Transfer Reactions from Nitrous Oxide

The synthesis and characterization of several zero‐valent cobalt complexes with a bis(olefin)‐amino ligand is presented. Some of these complexes proved to be efficient catalysts for the selective oxidation of secondary and allylic phosphanes, as well as diphosphanes, even with a direct P−P bond. With 5 mol % catalyst loadings the oxidations proceed under mild conditions (25–70 °C, 7–22 h, 2 bar N 2 O) and afford good to excellent yields (65–98 %). In this process, the greenhouse gas N 2 O is catalytically converted into benign N 2 and added‐value organophosphorus compounds, some of which are difficult to obtain otherwise.