Highly Selective Chromium(0)‐Mediated Insertion of Nitriles into a Nonpolar P–P Bond of a Substituted Hexahydro‐1,4‐diaza‐2,3,5,6‐tetraphosphorine

The cleavage of P–P σ bonds has long been a subject of interest and is investigated widely. P–P bonds can be cleaved homolytically to yield phosphinyl radicals, which can be persistent and stable for long periods or undergo further reactions. P–P bonds that exhibit polarization owing to different substitution can be opened heterolytically. Furthermore, it is possible to activate them through metal interactions. Both processes can be followed by the insertion of unsaturated small molecules into the homonuclear σ bonds. Herein, we present the versatile coordination behavior of a hexahydro‐1,4‐diaza‐2,3,5,6‐tetraphosphorine derivative to chromium carbonyls. Amongst other reactions, we observed a highly selective metal‐mediated insertion of a nitrile into an originally symmetrical P–P σ bond. The diverse coordination behavior of a hexahydro‐1,4‐diaza‐2,3,5,6‐tetraphosphorine derivative to chromium carbonyls is investigated. Homolytic P–P bond cleavage can be achieved through thermal stress to form a dinuclear phosphido‐bridged tricarbonyl chromium complex. A highly selective metal‐mediated bond cleavage followed by nitrile insertion is also found.