Neutral, cationic and anionic organonickel and -palladium complexes supported by iminophosphine/phosphinoenaminato ligands

Article abstract of DOI:10.1039/c9dt04062e

We report a series of organometallic nickel and palladium complexes containing iminophosphine ligands R₂PCH₂C(Ph) = N-Dipp (Dipp = 2,6-diisopropylphenyl; R = iPr, La; R = Ph, Lb; and R = o-C₆H₄OMe, Lc), synthesized by ligand exchange or oxidative addition reactions, and we investigate the capacity of such ligands to undergo reversible deprotonation to the corresponding phosphinoenaminato species. In the attempted ligand exchange reaction of the nickel bis(trimethylsilyl)methyl precursor [Ni(CH₂SiMe₃)₂Py₂] with Lb, the iminophosphine acts as a weak acid rather than a neutral ligand, cleaving one of the Ni-C bonds, to afford the phosphinoenaminato complex [Ni(CH₂SiMe₃)(L′b)(Py)] (L′b = conjugate base of Lb). We disclose a general method for the syntheses of complexes [Ni(CH₂SiMe₃)(L)(Py)]⁺ (L = La, Lb or Lc), and demonstrate that iminophosphine deprotonation is a general feature and occurs reversibly in the coordination sphere of the metal. By studying proton exchange reactions of the cation [Ni(CH₂SiMe₃)(Lb)(Py)]⁺ with bases of different strength we show that the conjugate phosphinoenaminato ligand in [Ni(CH₂SiMe₃)(L′b)(Py)] is a base with strength comparable to DBU in THF. The acyl group in the functionalized aryl complex [Ni(p-C₆H₄COCH₃)(Br)(La)] does not interfere in the iminophosphine deprotonation with NaH. The latter reaction affords the unusual anionic hydroxide species [Ni(p-C₆H₄COCH₃)(OH)(L′a)]^-Na⁺, which was isolated and fully characterized.