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)MCl2 complexes. Within these compounds, the diphosphine (iPr)DPDBFphos adapts a wide range of bite angles (115 to 180 degrees) as determined by X-ray crystallography. A three-coordinate planar Ni(I) species was isolated from the reduction of ((iPr)DPDBFphos)NiCl2 with KC8. 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 P-31 nuclei, A(iso) = 46 x 10(-4) cm(-1), and one Cl-37/Cl-38 nucleus, A = (12, 0.7, 35) x 10-4 cm-1. Density functional theory (DFT) studies reveal the nature of the magnetic orbital to be d(xy), which has sigma-antibonding and pi(parallel to)-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=CH2)Cl is generated along with the NO) dichloride complex. The monovalent Ni(I) chloride is an active catalyst in the Kumada cross-coupling reaction of vinyl chloride and phenyl Grignard reagent.