Reduction of the bis(iminopyridine) FeCl2 Complex 12,6-[2,6-(Pr-i)(2)PhN=C(CH3)](2)(C5H3N)}FeCl2 using NaH has led to the formation of a surprising variety of structures depending on the amount of reductant. Some of the species reported in this work were isolated from the same reaction mixture, and their structures suggest the presence of multiple pathways for dinitrogen activation. The reaction with 3 equiv of NaH afforded {2-[2,6-(Pr-i)(2)PhN=C(CH3)]-6-[2,6-(Pr-i)(2)PhN-C=CH2](C5H3N)}Fe(mu eta(2)-N-2)Na (THF) (1) containing one N-2 unit terminally bound to Fe and side-on attached to the Na atom. In the process, one of the two imine methyl groups has been deprotonated, transforming the neutral ligand into the corresponding monoanionic version. When 4 equiv were employed, two other dinitrogen complexes {2-[2,6-(Pr-i)(2)PhN=C(CH3)]-6-[2,6-(Pr-i)(2)PhN-C=CH2)(C5H3N)}Fe(mu-N-2 )Na(Et2O)(3) (2) and {2,6-[2,6-((i)pr)(2)PhN=C(CH3)](2)(C5H3N)Fe(mu-N-2)Na[Na(THF)(2)] (3) were obtained from the same reaction mixture. Complex 2 is chemically equivalent to 1, the different degree of solvation of the alkali cation being the factor apparently responsible for the sigma-bonding mode of ligation of the N-2 unit to Na, versus the pi-bonding mode featured in 1. In complex 3, the ligand remains neutral but a larger extent of reduction has been obtained, as indicated by the presence of two Na atoms in the structure. A further increase in the amount of reductant (12 equiv) afforded a mixture of {2-[2,6-(Pr-i)(2)PhN=C(CH3)]-6-[2,6-(Pr-i)(2)PhN-C=CH2)(C5H3N)}Fe-N-2 (4) and [{2,6-[2,6-(Pr-i)(2)PhN=C(CH3)]2-(C5H3N)}Fe-Ne-2](2)(mu-Na) [Na(THF)212 (5) which were isolated by fractional crystallization. Complex 4, also containing a terminally bonded N2 unit and a deprotonated anionic ligand bearing no Na cations, appears to be the precursor of 1. The apparent contradiction that excess NaH is required for its successful isolation (4 is the least reduced complex of this series) is most likely explained by the formation of the partner product 5, which may tentatively be regarded as the result of aggregation between 1 and 3 (with the ligand system in its neutral form). Finally, reduction carried out in the presence of additional free ligand afforded [2,6-[2,6-(Pr-i)(2)PhN=C(CH3)](2)(C5H3N)}Fe{eta(1)-N-2){2,6-[2,6-(Pr-i)( 2)PhN=C(CH3)](2)(NC5H2)}[Na(THF)(2)](6) and 2,6-[2,6-(Pr-i)(2)PhN=C(CH3)](2)(C5H3N)}Fe{2,6-[2,6-(Pr-i)(2)PhN= C(CH3)](2)(NC5H2)}Na(THF)(2)) (7). In both species, the Fe metal is bonded to the pyridine ring para position of an additional (L)Na unit. Complex 6 chemically differs from 7 (the major component) only for the presence of an end-on coordinated N2.