The synthesis of a series of iron and ruthenium complexes with the ligand (PP3Cy)-P-2, P(CH2CH2PCy2)(3) is described. The iron(0) and ruthenium(0) complexes Fe(N-2)((PP3Cy)-P-2) (1) and Ru(N-2)((PP3Cy)-P-2) (2) were synthesized by treatment of [FeCl((PP3Cy)-P-2)](+) and [RuCl((PP3Cy)-P-2)](+) with an excess of potassium graphite under a nitrogen atmosphere. The Fe(I) and Ru(I) species [Fe(N-2)((PP3Cy)-P-2)](+) (3) and RuCl((PP3Cy)-P-2) (4) were synthesized by treatment of [FeCl((PP3Cy)-P-2)](+) and [RuCl((PP3Cy)-P-2)](+) with 1 equiv of potassium graphite under a nitrogen atmosphere. The cationic dinitrogen species [Fe(N-2)H((PP3Cy)-P-2)](+) (6) and [Ru(N-2)H((PP3Cy)-P-2)](+) (7) were formed by treatment of 1 and 3, respectively, with I equiv of a weak organic acid. The iron(II) complex Fe(H)(2)((PP3Cy)-P-2) (5) was also synthesized and characterized. Complexes [RuCl((PP3Cy)-P-2)]-[BPh4], 1, 2, 3[BPh4], 4, 5, 6[BF4], and 7[BF4] were characterized by X-ray crystallography. The Fe(I) and Ru(I) complexes 3 and 4 were characterized by electron paramagnetic resonance (EPR) spectroscopy, and the Fe(I) complex has an EPR spectrum typical of a metal-centered radical.