has been prepared by the reaction of Li(DME)[P(t-Bu)2] with benzonitrile in 1,2-dimethoxyethan solution. The compound forms violet, moisture sensitive crystals, which were characterized by an X-ray structure determination [Space group P2 1 /n, Z = 4, 3282 observed unique reflections, R = 0.082. Lattice dimensions at -40°C: a = 851.0(5), b = 1238.0(3), c = 3029.2(4) pm, β = 90.53(4)°]. The compound forms an ion pair, in which the lithium atom is coordinated by two oxygen atoms of a chelating DME molecule, by an oxygen atom of a nonchelating DME molecule, and by the nitrogen atom of the planar diazaphosphole ring in 1-position. The phenyl groups are nearly coplanar with the diazaphosphole ring. is the product of the reaction of the lithium complex with methanol. It forms colourless crystals [Space group Ρ2 1 /n, Ζ = 4, 2015 observed unique reflections, R = 0.068. Lattice dimensions at -80°C: a = 1458.3(2), b = 824.8(1), c = 1716.9(2) pm, β = 105.37(9)°]. The molecules have planar 5 H-diazaphosphole rings.