The recently published purely metallo-organic Ni^I salt [Ni(cod)₂ ][Al(OR^F )₄ ] (1, cod=1,5-cyclooctadiene, R^F =C(CF₃ )₃ ) provides a starting point for a new synthesis strategy leading to Ni^I phosphine complexes, replacing cod ligands by phosphines. Clearly visible colour changes indicate reactions within minutes, while quantum chemical calculations (PBE0-D3(BJ)/def2-TZVPP) approve exergonic reaction enthalpies in all performed ligand exchange reactions. Hence, [Ni(dppp)₂ ][Al(OR^F )₄ ] (2, dppp=1,3-bis(diphenylphosphino)propane), [Ni(dppe)₂ ][Al(OR^F )₄ ] (3, dppe=1,3-bis(diphenyl-phosphino)ethane), three-coordinate [Ni(PPh₃ )₃ ][Al(OR^F )₄ ] (4) and a remarkable two-coordinate Ni^I phosphine complex [Ni(PtBu₃ )₂ ][Al(OR^F )₄ ] (5) were characterised by single crystal X-ray structure analysis. EPR studies were performed, confirming a nickel d⁹ -configuration in complexes 2, 4 and 5. This result is supported by additional magnetization measurements of 4 and 5. Further investigations by cyclic voltammetry indicate relatively high oxidation potentials for these Ni^I compounds between 0.7 and 1.7 V versus Fc/Fc⁺ . Screening reactions with O₂ and CO gave first insights on the reaction behaviour of the Ni^I phosphine complexes towards small molecules with formation of mixed phosphine-CO-Ni^I complexes and oxidation processes yielding new Ni^I and/or Ni^II derivatives. Moreover, 4 reacted with CH₂ Cl₂ at RT to give a dimeric Ni^II ylide complex (4 c). As CH₂ Cl₂ is a rather stable alkyl halide with relatively high C-Cl bond energies, 4 appears to be a suitable reagent for more general C-Cl bond activation reactions.

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