NI(ii) phosphine and phosphide complexes supported by a PNP-pyrrole pincer ligand

Abstract

The reaction between [(PN^pyrP)NiCl] (1, PN^pyrP = 2,5-bis((di-iso-propylphosphino)-methyl)-1H-pyrrolide) and TlPF₆ in the presence of a monodentate phosphine ligand led to cationic nickel phosphine and phosphite complexes, [(PN^pyrP)Ni(PHPh₂)][PF₆] (2), [(PN^pyrP)Ni(PMe₃)][PF₆] (3), and [(PN^pyrP)Ni{P(OMe)₃}][PF₆] (4). Compound 2 can be deprotonated resulting in the generation of a terminal phosphido complex, [(PN^pyrP)Ni(PPh₂)] (5). When 3 is subjected to a base, a methyl proton of PMe₃ is abstracted to afford [(PN^pyrP)Ni(CH₂PMe₂)] (6), containing a methylene bridge between Ni and the external phosphine. Compounds 2–6 were characterized by single crystal X-ray diffraction in addition to multi-nuclear NMR spectroscopy and elemental analysis.