A Phosphine-ss-diketiminate Nickel(I)-Complex for Small Molecule Activation

A bis(diphenyl)-phosphine functionalized ss-diketimine ligand (PNac-H) was applied for the synthesis of a subvalent Ni(I) complex [PNac-Ni]. Here, the Ni(I) center is stabilized by a tetradentate PNNP-type pocket, forming a square planar coordination sphere. Subsequently, the Ni(I) complex was investigated with regard to its reactivity and the activation of small molecules. The reductive potential of Ni(I) enabled an activation of different substrate classes, such as CH2X2 (X=Br, I), I-2 or Ph2E2 (E=S, Se). The ligand's design allows a stabilization of the reactive Ni(I) species while at the same time enabling activation processes due to a hemilabile coordination behavior and accessible axial coordination sites. The activation products have been characterized by single crystal X-ray diffraction, NMR and IR spectroscopy as well as elemental analysis.

Automated summary

A bis(diphenyl)-phosphine functionalized ss-diketimine ligand (PNac-H) was utilized for the synthesis of a subvalent Ni(I) complex [PNac-Ni]. The stability of the Ni(I) center was achieved through tetradentate PNNP-type coordination, resulting in a square planar coordination sphere. The reductive potential of Ni(I) allowed the activation of various substrates, and the ligand's design enabled both stabilization of the reactive Ni(I) species and activation processes due to its hemilabile coordination behavior and accessible axial coordination sites. The activation products were characterized using multiple analytical techniques.