This work describes a series of iron(II) phosphanylphosphido complexes. These compounds were obtained by reacting lithiated diphosphanes R2PP(SiMe3)Li (R = t-Bu, i-Pr) with an iron(II) beta-diketiminate complex, [LFe(mu(2)-cl)(2)Li(DME)(2)] (1) where DME = 1,2-dimethoxy- ethane and L = Dippnacnac (beta-diketiminate). While the reaction of 1 with t-Bu2PP(SiMe3)Li yields [LFe(n(1)-Me3SiPP-(t-Bu-2)] (2) that of 1 with equimolar amounts of i-Pr2PP(SiMe3)Li, in DME, leads to [LFe(n(2)-i-Pr2PPSiMe3)] (3). In contrast, the reaction of 1 with (i-Pr2N)(2)PP(SiMe3)Li provides not an iron-containing complex but 1[ (diisopropylamino)phosphine]-2,4-bis(diisopropylamino)-3(trimethylsilyl)tetraphosphetane (4). The structures of 2-4 were determined using diffractometry. Thus, 2 exhibits a three-coordinate iron site and 3 a four-coordinate iron site. The increase in the coordination number is induced by the change from an anticlinal to a synclinal conformation of the phoshpanylphosphido ligands. The electronic structures of 2 and 3 were assessed through a combined field-dependent Fe-57 Mossbauer and high frequency and-field electron paramagnetic resonance spectroscopic investigation in conjunction with analysis of their magnetic susceptibility and magnetization data. These studies revealed two high-spin iron(II) sites with S = 2 ground states that have different properties. While 2 exhibits a zero-field splitting described by a positive D parameter (D = +17.4 cm(-1); E/D = 0.11) for 3, this parameter is negative [D = 25(S) cm(-1); E/D = 0.15(5)]. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations provide insights into the origin of these differences and allow us to rationalize the fine and hyperfine structure parameters of 2 and 3. Thus, for 2, the spin orbit coupling mixes, a z(2)-type ground state with two low-lying {xz/yz} orbital states. These interactions lead to an easy plane of magnetization, which is essentially parallel to the plane defined by the N-Fe-N atoms. For 3, we find a yz-type ground state that is strongly mixed with a low-lying z(2)-type orbital state. In this case, the spin orbit interaction leads to a partial unquenching of the orbital momentum along the x axis, that is, to an easy axis of magnetization oriented roughly along the Fe P bond of the phosphido moiety.