Flash Communication: Rearrangement of a tris-Carbene Ligand Precursor to an all-N-Bound tris-Imidazole Iron Complex: Flipping the Umbrella

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-01-21 DOI:10.1021/acs.organomet.4c0044510.1021/acs.organomet.4c00445

Tom Hartmann, Lisa Pick, Frank W. Heinemann, Andreas Scheurer and Karsten Meyer*,

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Abstract

Treatment of the ligand precursor H₃TIMMN^MesCl₃ (TIMMN^Mes = tris-[(3-mesityl-imidazol-2-ylidene)methyl]amine) with an excess of base yields the literature-known ferrous tris-N-heterocyclic carbene (NHC) complex [(TIMMN^Mes)Fe^IICl]Cl (1-Cl). In contrast, utilizing a substoichiometric amount of base initiates a unique rearrangement of all three NHC pendant arms to yield the tripodal, all-N-bound tris-imidazole [(N-TIMMN^Mes)Fe^IICl]Cl (2-Cl_sol). Divalent 2-Cl and 2-PF₆ are fully characterized, structurally by single-crystal X-ray diffraction analysis and spectroscopically by ¹H NMR and ⁵⁷Fe Mössbauer spectroscopy as well as SQUID magnetization measurements, to demonstrate the influence of the change from a soft strong-field to a hard weak-field ligand. Optimized reaction conditions for the reproducible, high-yield carbene-to-imidazole rearrangement were developed in a series of experiments.

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.