NDLI: Testing the polynuclear hypothesis: multi-electron reduction of small molecules by triiron reaction sites

Content Provider	PubMed Central
Author	Powers, Tamara M. Betley, Theodore A.
Abstract	High-spin trinuclear iron complex (tbsL)Fe3(thf) ([tbsL]6− = [1,3,5- C6H9(NPh-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 (tbsL)Fe3(thf) yields triiron µ3-imido cluster (tbsL)Fe3(µ3-NH) and ammonia or aniline, respectively. (tbsL)Fe3(µ3-NH) has a similar zero-field 57Fe Mössbauer spectrum compared to previously reported [(tbsL)Fe3(µ3-N)]NBu4, and can be directly synthesized by protonation of the anionic triiron nitrido with lutidinium tetraphenylborate. Deprotonation of the triiron parent imido (tbsL)Fe3(µ3-NH) with lithium bis(trimethylsilyl)amide results in regeneration of the triiron nitrido complex capped with a thf-solvated Li cation [(tbsL)Fe3(µ3-N)]Li(thf)3. The lithium capped nitrido, structurally similar to the pseudo C 3-symmetric triiron nitride with a tetrabutylammonium counter cation, is rigorously C 3-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 (tbsL)Fe3(thf) affords (tbsL)Fe3(µ3-NPh) and aniline. The solid state structure of (tbsL)Fe3(µ3-NPh) is similar to the series of µ3-nitrido and -imido triiron complexes synthesized in this work with average Fe–Nimido and Fe–Fe bond lengths of 1.941(6) Å and 2.530(1) Å, respectively. Reductive N=N bond cleavage of azobenzene is also achieved in the presence of (tbsL)Fe3(thf) to yield triiron bisimido complex (tbsL)Fe3(µ3-NPh)(µ2-NPh), which has been structurally characterized. Ligand redox participation has been ruled out and, therefore, charge balance indicates that the bisimido cluster has undergone a 4e− metal based oxidation resulting in an (FeIV)(FeIII)2 formulation. Cyclic voltammograms of the series of triiron clusters presented herein demonstrate that oxidation states up to (FeIV)(FeIII)2 (in the case of [(tbsL)Fe3(µ3-N)]NBu4) are electrochemically accessible. These results highlight the efficacy of high-spin, polynuclear reaction sites to cooperatively mediate small molecule activation.
Related Links	http://dx.doi.org/10.1021/ja405057n
Ending Page	12296
Page Count	8
Starting Page	12289
File Format	PDF
ISSN	00027863
e-ISSN	15205126
Journal	Journal of the American Chemical Society
Issue Number	33
Volume Number	135
Language	English
Publisher Date	2013-08-21
Access Restriction	Open
Subject Keyword	Colloid and Surface Chemistry Biochemistry Chemistry(all) Catalysis Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Chemistry Colloid and Surface Chemistry Biochemistry Catalysis

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