We report here a thorough (1)H NMR study of Fe(acac)(2) solutions in a wide variety of noncoordinating and coordinating solvents, as well as the interaction of this complex with Et(3)N, pyridine, PMe(2)Ph, and R(2)PCH(2)CH(2)PR(2) [R = Ph (dppe), Et (depe)] in C(6)D(6). The study reveals that Fe(acac)(2) is readily transformed into Fe(acac)(3) in solution under aerobic conditions and that the commercial compound is usually contaminated by significant amounts of Fe(acac)(3). The (1)H NMR resonances of Fe(acac)(2) are rather solvent-dependent and quite different than those reported in the literature. The compound is unstable in CDCl(3) and stable in CD(2)Cl(2), C(6)D(6), CD(3)CN, acetone-d(6), DMSO-d(6), THF-d(8), and CD(3)OD. The addition of the above-mentioned ligands (L) reveals only one paramagnetically shifted band for each type of acac and L proton, the position of which varies with the L/Fe ratio, consistent with rapid ligand exchange equilibria on the NMR time scale. A fit of the NMR data at a high L/Fe ratio allows the calculation of the expected resonances for all protons in the Fe(acac)(2)L(2) molecules. The system with the bidentate depe ligand shows evidence for a slow ligand exchange at low depe/Fe ratios, proposed to involve a species with the cis-chelated mononuclear Fe(acac)(2)(depe) structure, whereas the fast exchange at a higher ratio is proposed to involved a trans-Fe(acac)(2)(κ(1)-depe)(2) complex. Complex Fe(acac)(2)(dppe) cannot be investigated in solution because of low solubility in a noncoordinating solvent and because of the poor dppe competition for binding in coordinating solvents. The compound was crystallized, and its X-ray structure reveals a 1-dimensional polymeric structure with dppe-bridged Fe centers having the trans-octahedral Fe(acac)(2)(κ(1)-dppe)(2) coordination environment.