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Controlling Reductive Elimination Pathways in Ti(IV) Pincer Complexes: Concerted versus Radical Mechanisms via Ligand

Paul Fritsche¹, Corinna Czernetzki¹, Maxi Liesa Heldner¹

¹Julius-Maximilians-Universität Würzburg, Institute of Inorganic Chemistry, Am Hubland, Würzburg 97074, Germany.

Journal of the American Chemical Society

|January 22, 2026

Summary

Researchers developed new titanium complexes for carbon-carbon bond formation via oxidatively induced reductive elimination (OIRE). They achieved selective alkyl radical expulsion and a rare, quantitative concerted reductive elimination, advancing early transition metal catalysis.

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Published on: November 20, 2014

Area of Science:

Organometallic Chemistry
Catalysis
Titanium Chemistry

Background:

Oxidatively induced reductive elimination (OIRE) is crucial for C-C bond formation, primarily in late transition metals.
Early transition metals, particularly titanium, are underexplored for OIRE reactions.
Controlling elementary steps like reductive elimination in titanium chemistry is challenging.

Purpose of the Study:

To explore the oxidation chemistry of novel pyridine-based titanium complexes.
To investigate the potential of titanium in OIRE reactions for C-C bond formation.
To achieve selective concerted reductive elimination from early transition metal complexes.

Main Methods:

Synthesis and characterization of two classes of pyridine-based titanium complexes.
Investigation of oxidation chemistry with varying ligands, organyls, and oxidants.
Utilizing quantum chemical calculations, electrochemical measurements, and crossover experiments to elucidate reaction mechanisms.

Main Results:

Demonstrated selective alkyl radical expulsion depending on ligand, organyl, and oxidant.
Achieved a rare, highly selective, and quantitative concerted reductive elimination from a titanium(IV) complex.
Identified that tridentate, redox-active ligands suppress one-electron pathways, favoring selective concerted reactivity.

Conclusions:

Appropriate ligand design is key to controlling reductive elimination in titanium chemistry.
This work advances the development of OIRE processes for early transition metals.
Achieved unprecedented control over a traditionally elusive elementary step in titanium catalysis.