Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands

Pérez-Bitrián, Alberto; Munárriz, Julen; Krause, Konstantin B.; Schlögl, Johanna; Hoffmann, Kurt F.; Sturm, Johanna S.; Hadi, Amiera N.; Teutloff, Christian; Wiesner, Anja; Limberg, Christian; Riedel, Sebastian

doi:10.1039/d4sc00543k

Chem. Sci.

2024

DOI: 10.1039/d4sc00543k

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Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands

Alberto Pérez-Bitrián,

Julen Munárriz,

Konstantin B. Krause

et al.

Abstract: Compounds containing Mn−O bonds are of utmost importance in biological systems and catalytic processes. Nevertheless, mononuclear manganese complexes containing all O-donor ligands are still rare. Taking advantage of the low...

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A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF₅)₃

Fischer,

Hoffmann,

Riedel

2024

Chemistry A European J

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The Lewis superacid Ga(OTeF5)3 has been synthesized and characterized, revealing a monomeric structure in solution and a dimeric structure in the solid state. Isolated adducts of Ga(OTeF5)3 with strong and weak Lewis bases have been characterized spectroscopically as well as single‐crystal X‐ray diffractometry. The Lewis acidity of this new species has been evaluated by means of different experimental and theoretical methods, which has allowed to classify it as one of only a few examples of a gallium‐based Lewis superacid. The high Lewis acidity of Ga(OTeF5)3 was used to amplify the strength of the Brønsted acid HOTeF5, leading to the protonation of diethyl ether. Furthermore, Ga(OTeF5)3 was utilized to access the strong oxidizing system Ga(OTeF5)3/Xe(OTeF5)2 in SO2ClF, which was successfully employed in the synthesis of the dimethyl chloronium salt [Cl(CH3)2][Ga(OTeF5)4], a strong electrophilic methylation reagent.

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A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF₅)₃

Fischer,

Hoffmann,

Riedel

2024

Chemistry A European J

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Deciphering Pyramidanes: A Quantum Chemical Topology Approach

Vidal,

Barrena‐Espés,

Echeverría

et al. 2024

ChemPhysChem

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C[C4H4], the simplest compound of the [4]‐pyramidane family, has so far eluded experimental characterization, although several of its analogs E[C4(SiMe3)4], in which the E apex atom is a tetrel group element, have been successfully prepared. The non‐classical bonding mode of E, similar to that found in propellanes, has prompted a considerable number of theoretical studies to unravel the nature of the apex‐base interaction. Here, we contribute to this knowledge by analyzing the electron localization function (ELF) and classical QTAIM descriptors; as well the statistical distribution of electrons in atomic regions by means of the so‐called electron distribution functions (EDFs), calculation of multicenter indices (MCI) as aromaticity descriptors and by performing orbital invariant energy decompositions with the interacting quantum atoms (IQA) approach on a series of E[C4(SiMe3)4] compounds. We find that the bonding evolves from covalent to electrostatic as E changes from C to Pb, with an anomaly when E=Si, which is shown to be the most charged moiety, compatible with an aromatic [C4(SiMe3)4]2‐ scaffold in the pyramidane base.

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Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands

Abstract: Compounds containing Mn−O bonds are of utmost importance in biological systems and catalytic processes. Nevertheless, mononuclear manganese complexes containing all O-donor ligands are still rare. Taking advantage of the low...

Cited by 2 publications

References 92 publications

A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF₅)₃

A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF₅)₃

Deciphering Pyramidanes: A Quantum Chemical Topology Approach

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Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands

Abstract: Compounds containing Mn−O bonds are of utmost importance in biological systems and catalytic processes. Nevertheless, mononuclear manganese complexes containing all O-donor ligands are still rare. Taking advantage of the low...

Cited by 2 publications

References 92 publications

A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF5)3

A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF5)3

Deciphering Pyramidanes: A Quantum Chemical Topology Approach

Contact Info

Product

Resources

About

A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF₅)₃

A Rare Example of a Gallium‐Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF₅)₃