title: First-row transition-metal chloride complexes of the wide bite-angle diphosphine (iPr)DPDBFphos and reactivity studies of monovalent nickel.
abstract: The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as (iPr)DPDBFphos) has been metalated with transition metal dichlorides of zinc, cobalt, and nickel to yield ((iPr)DPDBFphos)MCl(2) complexes. Within these compounds, the diphosphine (iPr)DPDBFphos adapts a wide range of bite angles (115 to 180°) as determined by X-ray crystallography. A three-coordinate planar Ni(I) species was isolated from the reduction of ((iPr)DPDBFphos)NiCl(2) with KC(8). Low-temperature electron paramagnetic resonance (EPR) measurements of ((iPr)DPDBFphos)NiCl allow the determination of g values (2.09, 2.14, 2.37) and hyperfine coupling constants to two (31)P nuclei, A(iso) = 46 × 10(-4) cm(-1), and one (37)Cl/(35)Cl nucleus, A = (12, 0.7, 35) × 10(-4) cm(-1). Density functional theory (DFT) studies reveal the nature of the magnetic orbital to be d(xy), which has σ-antibonding and π(∥)-antibonding interactions with the phosphorus and chloride atoms, respectively. The monovalent nickel complex reacts with substrates containing C-X bonds; and in the case of vinyl chloride, a Ni(II) vinyl species ((iPr)DPDBFphos)Ni(CH═CH(2))Cl is generated along with the Ni(II) dichloride complex. The monovalent Ni(I) chloride is an active catalyst in the Kumada cross-coupling reaction of vinyl chloride and phenyl Grignard reagent.
authors: Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States.
authors: Elodie E
authors: EE
authors: Marlier
authors: Stephen J
authors: SJ
authors: Tereniak
authors: Keying
authors: K
authors: Ding
authors: Jenna E
authors: JE
authors: Milliken
authors: Jenna E
authors: JE
authors: Mulliken
authors: Connie C
authors: CC
authors: Lu