Two 1,2,4-diazaphospholide complexes of [Ti(eta(2)-3,5-Ph(2)dp)(4)] and paramagnetic [Ti(eta(2)-3,5-tBu(2)dp)(3)] were prepared by the reaction of tetrakis-(dimethylamido)titanium(IV) with 3,5-diphenyl-1,2,4-diazaphophole, H[3,5-Ph(2)dp], or by the treatment of 3,5-tert-butyl-1,2,4-diazaphopholide potassium, K[3,5-tBu(2)dp], with titanium trichloride. Complexes can be viewed as the core of P(sigma(2)lambda(3))-functionalized metallodendrimers, in which the metal atoms are exclusively eta(2)(N,N) bonding to the 1,2,4-diazaphospholides while P atoms (sigma(2)lambda(3)) with electron lone pairs are located on the periphery of the molecules.