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Table · dataset · 2026

Directed Amination as a Strategy for C–N Bond Formation by Iron Imido Complexes

Listed in figshare and Loughborough Research Repository — shown once because both records carry DOI 10.1021/acs.inorgchem.6c01699.s002

The stabilization of low-coordinate and high-spin iron complexes plays a central role in enabling novel pathways for C–H functionalization and catalysis of organic reactions.

Description

Previous work from our group demonstrated that the bulky bis(carbene)borate ligand Ph<sub>2</sub>B(<sup><i>t</i></sup>BuIm)<sub>2</sub><sup>–</sup> supports the three-coordinate iron(II) imido complex [Ph<sub>2</sub>B(<sup><i>t</i></sup>BuIm)<sub>2</sub>Fe=NDipp]<sup>−</sup>.

In this study, we extend this platform by employing an even larger, more electron-withdrawing imido ligand to generate Ph<sub>2</sub>B(<sup><i>t</i></sup>BuIm)<sub>2</sub>Fe(N(terph)) (terph = 2,6-C<sub>6</sub>H<sub>5</sub>(C<sub>6</sub>H<sub>3</sub>)). This iron(III) imido complex was isolated and fully characterized, including by single-crystal X-ray diffraction. The complex reacts with 2-picoline to afford C–N bond functionalization at the benzylic position of the substrate.

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Mechanistic investigations by density functional theory calculations support a pathway in which intramolecular hydrogen atom transfer from the coordinated substrate to the imido ligand provides a carbon-centered radical. Subsequent intramolecular radical rebound forms a new C–N bond. Together, these two steps define a mechanistic sequence reminiscent of enzymatic C–H functionalization pathways at a well-defined, low-coordinate iron complex.

In addition, DFT provides insight into the directing effect of the picoline ligand.

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Astronomy & Astrophysics · Cancer · Cancer · Chemistry · Chemistry · Computer Science & AI · Computer Science & AI · Earth & Environmental Science · Earth & Environmental Science · Economics & Finance · Economics & Finance · Engineering · Engineering · Humanities · Humanities · Infectious diseases · Infectious diseases · Life Sciences · Life Sciences · Materials Science · Mathematics & Statistics · Medicine & Health · Medicine & Health · Ocean & Atmospheric Science · Psychology & Behavioral Science · Social Science · Social Science
Inferred from text
Density functional theory 75%
Provenance · 2 source records, 33 field assertions
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figshareoai:figshare.com:article/3396074210 d agoJSON v1
Loughborough Research Repositoryoai:figshare.com:article/339607429 d agoJSON v1
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