Isocyanide Substituent Influences Reductive Elimination versus Migratory Insertion in Reaction with an [Fe2(μ-H)2]2+ Complex
Iron hydrides are proposed reactive intermediates for N2 and CO conversion in industrial and biological processes. Here, we report a reactivity study of a low-coordinate di(μ-hydrido)diiron(II) complex, Fe2(μ-H)2 L, where L 2– is a bis(β-diketiminate) cyclophane, with isocyanides, which have ele...
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Veröffentlicht in: | Inorganic chemistry 2024-11, Vol.63 (44), p.21083-21091 |
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Hauptverfasser: | , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Iron hydrides are proposed reactive intermediates for N2 and CO conversion in industrial and biological processes. Here, we report a reactivity study of a low-coordinate di(μ-hydrido)diiron(II) complex, Fe2(μ-H)2 L, where L 2– is a bis(β-diketiminate) cyclophane, with isocyanides, which have electronic structures related to N2 and CO. The reaction outcome is influenced by the isocyanide substituent, with 2,6-xylyl isocyanide leading to H2 loss, to form a bis(μ-1,1-isocyanide)diiron(I) complex, whereas all of the other tested isocyanides insert into the Fe–H bond to give (μ-1,2-iminoformyl) complexes. Steric bulk of the isocyanide substituent determines the extent of insertion (i.e., into one or both Fe–H–Fe units) with tert-butyl isocyanide reacting to yield the mono-(μ-1,2-iminoformyl)diiron(II) complex, exclusively, and isopropyl- and methyl isocyanides affording the bis(μ-1,2-iminoformyl)diiron(II) products. Treatment of Fe2(μ-1,2-CHNtBu)(μ-H)L with 2,6-xylyl isocyanide (or XylNC) yields Fe2(μ-XylNC)2 L and tert-butylaldimine as one of the organic products. |
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ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/acs.inorgchem.4c03256 |