Disauerstoffaktivierung und Pyrrol‐α‐Spaltung mit Calix[4]pyrrolatoaluminaten: Enzymmodell durch strukturellen Zwang

Sigmund, Lukas M.; Ehlert, Christopher; Enders, Markus; Graf, Jürgen; Gryn’ova, Ganna; Greb, Lutz

doi:10.1002/ange.202104916

Cited by 7 publications

(1 citation statement)

References 99 publications

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“…Examples of structurally constrained tetracoordinate (square planar) group 13 complexes are rare (Figure 1). [15–19] However, those reported remain appreciably Lewis acidic due to their unusual geometry and exhibit MLC reactivity [20–25] . We proposed that using an appropriate pincer ligand could induce Lewis acidity at aluminium by structural constraint and the formation of a nucleophilic ligand site to promote MLC reactivity.…”

Section: Introductionmentioning

confidence: 99%

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO₂

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Villegas‐Escobar

Clark

et al. 2023

Chemistry A European J

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The use of a sterically demanding pincer ligand to prepare an unusual square planar aluminium complex is reported. Due to the constrained geometry imposed by the ligand scaffold, this four-coordinate aluminium centre remains Lewis acidic and reacts via differing metal-ligand cooperative pathways for activating ketones and CO 2 . It is also a rare example of a single-component aluminium system for the catalytic reduction of CO 2 to a methanol equivalent at room temperature.

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Section: Introductionmentioning

confidence: 99%

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO₂

Shaves

Villegas‐Escobar

Clark

et al. 2023

Chemistry A European J

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Calix[4]pyrrolatostannat(II): Ein Tetraamidozinn(II)dianion als starker, metallzentrierter σ‐Donor

Ruppert

Greb

2022

Angewandte Chemie

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Anionische, metallzentrierte Nukleophile sind Verbindungen mit einzigartigen Reaktivitäten. In dieser Arbeit beschreiben wir die Isolierung und vollständige Charakterisierung des ersten Tetraamidozinn(II)dianions, sein Verhalten als Ligand gegenüber Übergangsmetallen und seine Reaktivität als zinnzentriertes Nukleophil. Experimentelle Werte wie der elektronische Tolman Parameter (TEP) und quantenchemische Berechnungen bescheinigen dem Zinn eine σ-Donorfähigkeit, welche die von Carbenen oder elektronenreichen Phosphinen übertrifft. Gegenüber Übergangsmetallen kann das Stannat(II) als η 1 -oder η 5 -Ligand wirken. Mit Aldehyden reagiert es unter Hydridsubstitution zu wertvollen Acylstannaten(IV). Die reduktive Dehalogenierung von Iodbenzol weist auf zugängliche Redoxwege hin, welche durch die Wechselwirkung mit Halogenbindungen vermittelt werden. Calix[4]pyrrolatostannat(II) [2] 2 ist das erste Beispiel niedervalenter p-Block-Elementkomplexe der Calix[4]pyrrole.

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Calix[4]pyrrolato Aluminate Catalyzes the Dehydrocoupling of Phenylphosphine Borane to High Molar Weight Polymers

et al. 2022

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High molar weight polyphosphinoboranes represent materials with auspicious properties, but their preparation requires transition metal-based catalysts. Here, calix[4]pyrrolato aluminate is shown to induce the dehydropolymerization of phosphine boranes to high molar mass polyphosphinoboranes (up to M n = 43 000 Da). Combined GPC and 31 P DOSY NMR spectroscopic analyses, quantum chemical computations, and stoichiometric reactions disclose a PÀ H bond activation by the cooperative action of the square-planar aluminate and the electron-rich ligand framework. This first transition metal-free catalyst for PÀ B dehydrocoupling overcomes the problem of residual d-block metal impurities in the resulting polymers that might interfere with the reproducibility of the properties for this emerging class of inorganic materials.

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Disauerstoffaktivierung und Pyrrol‐α‐Spaltung mit Calix[4]pyrrolatoaluminaten: Enzymmodell durch strukturellen Zwang

Cited by 7 publications

References 99 publications

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO₂

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO₂

Calix[4]pyrrolatostannat(II): Ein Tetraamidozinn(II)dianion als starker, metallzentrierter σ‐Donor

Calix[4]pyrrolato Aluminate Catalyzes the Dehydrocoupling of Phenylphosphine Borane to High Molar Weight Polymers

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Disauerstoffaktivierung und Pyrrol‐α‐Spaltung mit Calix[4]pyrrolatoaluminaten: Enzymmodell durch strukturellen Zwang

Cited by 7 publications

References 99 publications

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO2

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO2

Calix[4]pyrrolatostannat(II): Ein Tetraamidozinn(II)dianion als starker, metallzentrierter σ‐Donor

Calix[4]pyrrolato Aluminate Catalyzes the Dehydrocoupling of Phenylphosphine Borane to High Molar Weight Polymers

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Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO₂

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO₂