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oai:figshare.com:article/33960742 2026-09-22T03:07:44Z category_1 category_4 category_915 category_14 category_21 category_873 category_64 category_132 portal_63 item_type_3 month_year_09_2026

Directed Amination as a Strategy for C–N Bond Formation by Iron Imido Complexes Arya Sreeja Ajay (25086283) Spencer Cole Hanna (25086286) Maren Pink (1340589) Nobuyuki Yamamoto (411767) Eric D. Bloch (1408648) Jeremy M. Smith (187646) Biophysics Biochemistry Physical Sciences not elsewhere classified Molecular Biology Biotechnology Chemical Sciences not elsewhere classified Cancer Infectious Diseases two steps define enabling novel pathways dft provides insight mechanistic sequence reminiscent withdrawing imido ligand imido ligand provides buim )< sub iron imido complexes borate ligand ph 2 </ sub 6 </ sub coordinate iron complex imido complex mechanistic investigations picoline ligand coordinate iron complex reacts ray diffraction previous work organic reactions group demonstrated generate ph fully characterized even larger directing effect directed amination crystal x central role centered radical bulky bis benzylic position ></ sup 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. Previous work from our group demonstrated that the bulky bis(carbene)borate ligand Ph₂B(^<i>t</i>BuIm)₂^– supports the three-coordinate iron(II) imido complex [Ph₂B(^<i>t</i>BuIm)₂Fe=NDipp]⁻. In this study, we extend this platform by employing an even larger, more electron-withdrawing imido ligand to generate Ph₂B(^<i>t</i>BuIm)₂Fe(N(terph)) (terph = 2,6-C₆H₅(C₆H₃)). 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. 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. 2026-09-21T00:00:00Z Dataset Dataset 10.1021/acs.inorgchem.6c01699.s002 https://figshare.com/articles/dataset/Directed_Amination_as_a_Strategy_for_C_N_Bond_Formation_by_Iron_Imido_Complexes/33960742 CC BY-NC 4.0