Synthesis and characterization of novel organonickel and organocobalt complexes via carbon–chlorine bond activation

•C–Cl bond activation mediated by nickel and cobalt complexes.•ortho-Metalation of ortho-halogeno aromatic diimine by nickel and cobalt complexes.•Electron-rich low-valent nickel and cobalt complexes supported by trimethylphosphine.

The ortho-metalated nickel(II) complexes 3, 4, 7 and 8 were obtained by the reaction of ortho-halogeno aromatic bis-Schiff bases 1, 2, 5 and 6 with the stoichiometric amount of Ni(PMe3)4. The combination of 5 and 6 with two equivalents of Ni(PMe3)4 resulted in oxidative addition of the double C–Cl bonds to afford ortho-bis-chelated nickel(II) complexes 9 and 10. The reaction of 6 with Co(PMe3)4 gave rise to di-nuclear ortho-metalated cobalt(II) complex 12 through C–Cl bond activation while the reaction of 5 with Co(PMe3)4 delivered bis-chelated cobalt(I) complex 11 through both C–Cl and C–H bond activation. The structures of complexes 3, 4, 8, 9, 11 and 12 were determined by X-ray single crystal diffraction. The catalytic activity of bis-chelated cobalt(I) complex 11 as catalyst for C,C-coupling reaction was explored.

Graphical abstractReaction of ortho-chlorodiimine 5 with Co(PMe3)4 delivered complex 11 via C–Cl/C–H activation. Catalytic activity of 11 for C,C-coupling was explored.Figure optionsDownload full-size imageDownload as PowerPoint slide