The bdt-bridged diiron-amide complex [Cp*Fe(mu-eta(2):eta(2)-bdt)(mu-NH2)FeCp*][BF4](2) (1[BF4](2), Cp* = eta(5)-C5Me5; bdt = benzene-1,2-dithiolate) and its reduction products [Cp*Fe(mu-n(2):eta(2)-bdt)(mu-NH2) FeCp*][BF4] (2[BE4]) and [Cp*Fe(mu-n(2):eta(1)-bdt)(mu-NH2)FeCP*] (3) have been synthesized. OFT calculations suggest that the sequential reduction of 1[BF4](2) to 2[BF4] and further to 3 is a bimetal and single metal based process, respectively. The ground state of 1[BF4](2) is predicted to be quartet. 2[BF4] has an antiferromagnetic coupling BS(1,1) ground state, and the ground state of 3 is proposed to be BS(1,0). The bdt ligand in these three complexes is better viewed as a dianion ligand rather than a monoanionic radical. (C) 2016 Elsevier B.V. All rights reserved.