Nitrogenase Model Complexes [Cp*Fe(μ-SR1)2(μ-η2-R2N═NH)FeCp*] (R1 = Me, Et; R2 = Me, Ph; Cp* = η5-C5Me5): Synthesis, Structure, and Catalytic N−N Bond Cleavage of Hydrazines on Diiron Centers

The reactions of [Cp*Fe(mu-SR1)3FeCp*] (Cp* = eta5-C5Me5; R1 = Et, Me) with 1.5 equiv R2NHNH2 (R2 = Ph, Me) give the mu-eta2-diazene diiron thiolate-bridged complexes [Cp*Fe(mu-SR1)2(mu-eta2-R2N NH)FeCp*], along with the formation of PhNH2 and NH3. These mu-eta2-diazene diiron thiolate-bridged complexes exhibit excellent catalytic N-N bond cleavage of hydrazines under ambient conditions.