Lithium bis(o-anisyl)phosphide (1) may be prepared by reaction of n-BuLi with bis(o-anisyl)phosphine in THF or toluene; sodium bis(o-anisyl)phosphide (2) is prepared by reaction of sodium with tris(o-anisyl)phosphine in liquid ammonia/THF; both compounds are isolated as unsolvated solids. 1 decomposes quantitatively in THF to give tetrakis(o-anisyl)diphosphine (4); 2 decomposes in THF to give a mixture containing 4 and bis(o-anisyl)phosphine. Addition of diglyme to 2 gives [Na{mu-P(C(6)H(4)OMe-o)(2)}(MeO(CH2CH2O)(2)Me)](2) (2a), which has been characterized by single-crystal X-ray diffraction, Each Na atom in 2a is 6-coordinate, being bonded to two P atoms, three diglyme O atoms, and one O atom from an o-anisyl group. Crystal data : monoclinic, P2(1)/n, a = 14.549(4) Angstrom, b = 18.555(6) Angstrom, c = 15.846(4) Angstrom, beta = 91.07(2)degrees, Z = 4, final R = 0.041, R(w) = 0.053.