The synthesis of rare anionic heteroleptic and homoleptic alpha-diimine iron complexes is described. Heteroleptic BIAN (bis(aryl)iminoacenaphthene) complexes 1-[K([18]c-6)-(thf)(0.5)] and 2-[K([18]c-6)(thf)(2)] were synthesized by reduction of the [(BIAN)FeBr2] precursor complex using stoichiometric amounts of potassium graphite in the presence of the corresponding olefin. The electronic structure of these paramagnetic species was investigated by numerous spectroscopic analyses (NMR, EPR, Fe-57 Mossbauer, UV-vis), magnetic measurements (Evans NMR method, SQUID), and theoretical techniques (DFT, CASSCF). Whereas anion 1 is a low-spin complex, anion 2 consists of an intermediate-spin Fe(III) center. Both complexes are efficient precatalysts for the hydroboration of carbonyl compounds under mild reaction conditions. The reaction of bis(anthracene) ferrate(1-) gave the homoleptic BIAN complex 3-[K([18]c-6)(thf)], which is less catalytically active. The electronic structure was elucidated with the same techniques as described for complexes 1-[K([18]c-6)(thf)(0.5)] and 2-[K([18]c-6)(thf)(2)] and revealed an Fe(II) species in a quartet ground state.