2015
DOI: 10.1021/acs.inorgchem.5b00825
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Nitride-Bridged Triiron Complex and Its Relevance to Dinitrogen Activation

Abstract: Using a simple metathesis approach, the triiron(II) tribromide complex Fe3Br3L (1) reacts with tetrabutylammonium azide to afford the monoazide dibromide analogue Fe3(Br)2(N3)L (2) in high yield. The inclusion of azide was confirmed by IR spectroscopy with a ν(N3) = 2082 cm(-1) as well as combustion analysis and X-ray crystallography. Heating 2 in the solid state results in the complete loss of the azide vibration in the IR spectra and the isolation of the olive-green mononitride complex Fe3(Br)2(N)L (3). Solu… Show more

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Cited by 31 publications
(20 citation statements)
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“…Whereas those reactions do not involve changes in the oxidation state of the metal precursor, a second general procedure, and most appropriate for nitrido clusters of mid and late transition metals, is the reduction of an oxidized nitrogen source with a low-valent metal center or a reduced co-ligand. For instance, treatment of low-valent metal precursors with azides [49,67] or reduction of nitrosyl ligands appended to metal clusters [15] are typical entries to polymetallic species with n-N ligands. Of particular relevance in the field of nitrogen fixation is the cleavage of dinitrogen by reduced complexes to afford nitrido ligands.…”
Section: Common Synthetic Routesmentioning
confidence: 99%
“…Whereas those reactions do not involve changes in the oxidation state of the metal precursor, a second general procedure, and most appropriate for nitrido clusters of mid and late transition metals, is the reduction of an oxidized nitrogen source with a low-valent metal center or a reduced co-ligand. For instance, treatment of low-valent metal precursors with azides [49,67] or reduction of nitrosyl ligands appended to metal clusters [15] are typical entries to polymetallic species with n-N ligands. Of particular relevance in the field of nitrogen fixation is the cleavage of dinitrogen by reduced complexes to afford nitrido ligands.…”
Section: Common Synthetic Routesmentioning
confidence: 99%
“…Synthetic mid‐valent iron nitride complexes may permit better elucidation of potential ligand behaviour of nitride associated with dinitrogen activation process. Yet introduction of nitride into mid‐valent iron complexes continues to prove a challenge …”
Section: Methodsmentioning
confidence: 99%
“…nitridotriiron bromide cyclophanates. 65 Dinitrogen binding is not observed to members of the series, Fe 3 ( μ 3 -N)Br x L Et/Me (x = 0, 1, or 2), but chemical reduction of these compounds results in dinitrogen activation ( vide infra) , supporting an intercluster pathway as possible.…”
Section: Cyclophane-based Ligand (H3let/me)mentioning
confidence: 99%
“…Insofar as intermediates upon reduction of Fe 3 Br 3 L Et/Me remain elusive, we instead sought to benchmark the reactivity of possible intercluster intermediates, namely, nitridotriiron bromide cyclophanates. 65 Dinitrogen binding is not observed to members of the series, Fe 3 (μ 3 -N)Br x L Et/Me (x = 0, 1, or 2), but chemical reduction of these compounds results in dinitrogen activation (vide infra), supporting an intercluster pathway as possible.…”
Section: Small Molecule Activation Using Trimetallic Complexesmentioning
confidence: 99%
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