Testing the polynuclear hypothesis: multielectron reduction of small molecules by triiron reaction sites.

High-spin trinuclear iron complex ((tbs)L)Fe3(thf) ([(tbs)L](6-) = [1,3,5-C6H9(NC6H4-o-NSi(t)BuMe2)3](6-)) (S = 6) facilitates 2 and 4e(-) reduction of NxHy type substrates to yield imido and nitrido products. Reaction of hydrazine or phenylhydrazine with ((tbs)L)Fe3(thf) yields triiron μ(3)-imido cluster ((tbs)L)Fe3(μ(3)-NH) and ammonia or aniline, respectively. ((tbs)L)Fe3(μ(3)-NH) has a similar zero-field (57)Fe Mössbauer spectrum compared to previously reported [((tbs)L)Fe3(μ(3)-N)]NBu4, and can be directly synthesized by protonation of the anionic triiron nitrido with lutidinium tetraphenylborate. Deprotonation of the triiron parent imido ((tbs)L)Fe3(μ(3)-NH) with lithium bis(trimethylsilyl)amide results in regeneration of the triiron nitrido complex capped with a thf-solvated Li cation [((tbs)L)Fe3(μ(3)-N)]Li(thf)3. The lithium capped nitrido, structurally similar to the pseudo C3-symmetric triiron nitride with a tetrabutylammonium countercation, is rigorously C3-symmetric featuring intracore distances of Fe-Fe 2.4802(5) Å, Fe-N(nitride) 1.877(2) Å, and N(nitride)-Li 1.990(6) Å. A similar 2e(-) reduction of 1,2-diphenylhydrazine by ((tbs)L)Fe3(thf) affords ((tbs)L)Fe3(μ(3)-NPh) and aniline. The solid state structure of ((tbs)L)Fe3(μ(3)-NPh) is similar to the series of μ(3)-nitrido and -imido triiron complexes synthesized in this work with average Fe-Nimido and Fe-Fe bond lengths of 1.941(6) and 2.530(1) Å, respectively. Reductive N═N bond cleavage of azobenzene is also achieved in the presence of ((tbs)L)Fe3(thf) to yield triiron bis-imido complex ((tbs)L)Fe3(μ(3)-NPh)(μ(2)-NPh), which has been structurally characterized. Ligand redox participation has been ruled out, and therefore, charge balance indicates that the bis-imido cluster has undergone a 4e(-) metal based oxidation resulting in an (Fe(IV))(Fe(III))2 formulation. Cyclic voltammograms of the series of triiron clusters presented herein demonstrate that oxidation states up to (Fe(IV))(Fe(III))2 (in the case of [((tbs)L)Fe3(μ(3)-N)]NBu4) are electrochemically accessible. These results highlight the efficacy of high-spin, polynuclear reaction sites to cooperatively mediate small molecule activation.