Tripodal silanolate ligands expand MoX3 chemistry beyond its traditional borders & synthetic strategies for diamagnetic iron carbenes
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Date
2025
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Abstract
Dimer formation is the signature reactivity of Mo+III complexes, shaping their unique chemical identity. While a myriad of homodimeric Mo+III complexes are well documented in the literature, only a small number of monomeric Mo+III complexes has been reported. Typically, either the monomeric or homodimeric form is obtained depending on the steric bulk of the supporting ligand. In this doctoral thesis, the prevailing paradigm was successfully challenged by synthesizing, for the first time, monomeric, homodimeric, and previously unknown heterodimeric complexes, all incorporating the same ligand. Notably, the resulting monomer can activate small molecules such as N2O and 1,1-dichloropropane. An in-depth analysis of the electronic structure of the heterodimeric complex was conducted using 95Mo NMR spectroscopy and DFT calculations.
In the second part of this thesis, various strategies for the synthesis of iron carbenes were explored. One of these is the Binger rearrangement strategy, which involves the formal electrocyclic ring-opening of a strained cyclopropene to generate a transition metal alkenyl carbene. This strategy proved successful in the present work, enabling the isolation of an alkenyl iron carbene. Conventional analytical tools were complemented by 57Fe NMR spectroscopy, a technique that is highly challenging due to the unfavorable properties of the 57Fe nucleus.
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Keywords
Silanolat-Liganden, Mo(III)-Chemie, Eisen-Carbene
Subjects based on RSWK
Silicium, Carbene