The first neutral four-coordinate selenolato iron(II) complexes, Fe(Se-2,6-i-Pr2C6H3)(2)(PMe(2)Ph)(2), 1, and Fe(Se-2,6-i-Pr2C6H3)(2)(Et(2)PCH(2)CH(2)PEt(2)), 2, are prepared by metathesis of chloride ligands of iron(II) chloride with selenolate in the presence of 2 equiv of dimethylphenylphosphine or 1 equiv of 1,2-bis(diethylphosphino)ethane, respectively. The room temperature magnetic moment of both 1 and 2 is about 5 mu(B) as determined both in the solid state and in solution. The proton NMR spectra exhibit paramagnetic shifts and broadening associated with the unpaired electron density at the metal center. The spectra were completely assigned using integration and linewidth information. Cyclic voltammetry and electronic spectra of 1 and 2 and the Mossbauer spectrum of 1 are also reported. Single crystal X-ray diffraction studies at 296 K revealed a crystallographically imposed C-2 symmetry for 1. The coordination geometry about the iron centers is distorted tetrahedral for both complexes. The Se-Fe-Se angle is much larger than tetrahedral with a value of about 130 degrees for both complexes. Fe(Se-2,6-i-Pr2C6H3)(2)(PMe(2)Ph)(2), 1, crystallizes in the monoclinic space group C2/c with a = 22.330(4), b = 12.485(2), c = 16.667(3) Angstrom, beta = 118.03(3)degrees, Z = 4, V = 4101.6(12) Angstrom(3), d(calc) = 1.316 g cm(-3), R = 0.0431, R(w) = 0.0551. Fe(Se-2,6-i-Pr2C6H3)(2)(depe), 2, crystallizes in the monoclinic space group P2(1)/n with a = 9.418(1), b = 19.484(4), c = 20.631(3) Angstrom, beta = 93.79(1)degrees, Z = 4, V = 3777.5(13) Angstrom(3), d(calc) = 1.306 g cm(-3), R = 0.0529, R(w) = 0.0626.