A Modular Approach to Asymmetric Mg(I) Complexes Using a Unique Cyclopentadienyl Mg(I) Complex

Stecher H, Thum S, Maurer J, Mai J, Schmidt M, Langer J, Harder S (2025)

Publication Type: Journal article

Publication year: 2025

Journal

Angewandte Chemie International Edition Wiley

DOI: 10.1002/anie.202518538

Abstract

The first MgI complexes with non-N ligands have been isolated and were fully characterized. Reaction of [(BDI*)MgNa]2 (III) with MgCp*2 gave quantitative conversion to (BDI*)MgMgCp* (1); BDI* = HC[tBuC = N(DIPeP)]2, DIPeP = 2,6-Et2CH-phenyl) and Cp* = pentamethylcyclopentadienyl. A similar reaction with CaCp*2 did not give (BDI*)MgCaCp* but led to insertion of the formal Mg° centre in the benzylic C─H bond, an oxidative addition that resulted in a mixed Mg/Ca hydride complex. The Cp* ligand in the unique (BDI*)MgMgCp* complex can be exchanged by addition of LM (M = Li, Na, K) complexes, resulting in formation of (BDI*)MgMgL and insoluble (Cp*M)n. This modular approach worked for Cp*/N(SiMe3)2 exchange but not for the substitution of Cp* by P(SiMe3)2 or other PR2 ligands. Reaction of (BDI*)MgMgCp* with a bulky NaOAr reagent led to quantitative formation of (BDI*)MgMgOAr·THF, a first MgI complex stabilized with an aryloxide ligand. All products have been fully characterized by X-ray diffraction and NMR methods. A computational study gives insight in the thermodynamics of formation and electronic structures.

Authors with CRIS profile

Hannah Stecher Lehrstuhl für Anorganische und Metallorganische Chemie Stefan Thum Lehrstuhl für Anorganische und Metallorganische Chemie Johannes Maurer Lehrstuhl für Anorganische und Metallorganische Chemie Jonathan Mai Lehrstuhl für Anorganische und Metallorganische Chemie Marcel Schmidt Lehrstuhl für Anorganische und Metallorganische Chemie Jens Langer Lehrstuhl für Anorganische und Metallorganische Chemie Sjoerd Harder Lehrstuhl für Anorganische und Metallorganische Chemie

How to cite

APA:

Stecher, H., Thum, S., Maurer, J., Mai, J., Schmidt, M., Langer, J., & Harder, S. (2025). A Modular Approach to Asymmetric Mg(I) Complexes Using a Unique Cyclopentadienyl Mg(I) Complex. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.202518538

MLA:

Stecher, Hannah, et al. "A Modular Approach to Asymmetric Mg(I) Complexes Using a Unique Cyclopentadienyl Mg(I) Complex." Angewandte Chemie International Edition (2025).

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