Iron(I) and Iron(II) Amido-imidazolin-2-imine Complexes as Catalysts for H/D Exchange in Hydrosilanes
The unsymmetrical amino-imidazolin-2-imine ligand [HAmIm, 1,2-(DippNH)–C6H4–N=C(NiPrCMe)2] is employed in the synthesis of the iron(I) arene complex [(AmIm)Fe(η 6 -C6H6)] and the iron(II) neosilyl complex [(AmIm)Fe(CH2SiMe3)]. These compounds are highly efficient precatalysts in H/D exchange...
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Published in | ACS catalysis Vol. 14; no. 3; pp. 1759 - 1772 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
02.02.2024
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Subjects | |
Online Access | Get full text |
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Summary: | The unsymmetrical amino-imidazolin-2-imine ligand [HAmIm, 1,2-(DippNH)–C6H4–N=C(NiPrCMe)2] is employed in the synthesis of the iron(I) arene complex [(AmIm)Fe(η 6 -C6H6)] and the iron(II) neosilyl complex [(AmIm)Fe(CH2SiMe3)]. These compounds are highly efficient precatalysts in H/D exchange reactions with deuterium (D2) in hydrosilanes. The scope comprises primary to tertiary silanes at a catalyst loading of 1 mol % at ambient temperature. In-depth mechanistic studies including various control experiments and the syntheses of isolated iron-hydride and iron-silyl compounds are performed. These studies reveal that the activation of both Fe(I) and Fe(II) complexes generates Fe–H/D species as key catalytic intermediates. An alternative catalytic pathway involving an iron-silyl intermediate, although shown to be less feasible by DFT calculations, may also be operative. |
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ISSN: | 2155-5435 2155-5435 |
DOI: | 10.1021/acscatal.3c05355 |