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 N2O) and afford good to excellent yields (65–98 %). In this process, the greenhouse gas N2O is catalytically converted into benign N2 and added‐value organophosphorus compounds, some of which are difficult to obtain otherwise. Utilizing greenhouse gas: A series of zero valent amino olefin cobalt complexes is used to convert phosphanes into phosphane oxides with N2O. N2 is the only side product. The catalytic transformation proved to be efficient and selective for a large variety of substrates including highly sensitive phosphanes, such as secondary, vinylic, or diphosphanes with P−P bonds.