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Metal-Ligand Cooperativity of the Calix[4]pyrrolato Aluminate: Triggerable C-C Bond Formation and Rate Control in Catalysis.


ABSTRACT: Metal-ligand cooperativity (MLC) had a remarkable impact on transition metal chemistry and catalysis. By use of the calix[4]pyrrolato aluminate, [1]- , which features a square-planar AlIII , we transfer this concept into the p-block and fully elucidate its mechanisms by experiment and theory. Complementary to transition metal-based MLC (aromatization upon substrate binding), substrate binding in [1]- occurs by dearomatization of the ligand. The aluminate trapps carbonyls by the formation of C-C and Al-O bonds, but the products maintain full reversibility and outstanding dynamic exchange rates. Remarkably, the C-C bonds can be formed or cleaved by the addition or removal of lithium cations, permitting unprecedented control over the system's constitutional state. Moreover, the metal-ligand cooperative substrate interaction allows to twist the kinetics of catalytic hydroboration reactions in a unique sense. Ultimately, this work describes the evolution of an anti-van't Hoff/Le Bel species from their being as a structural curiosity to their application as a reagent and catalyst.

SUBMITTER: Ebner F 

PROVIDER: S-EPMC7540271 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Metal-Ligand Cooperativity of the Calix[4]pyrrolato Aluminate: Triggerable C-C Bond Formation and Rate Control in Catalysis.

Ebner Fabian F   Sigmund Lukas Maximilian LM   Greb Lutz L  

Angewandte Chemie (International ed. in English) 20200818 39


Metal-ligand cooperativity (MLC) had a remarkable impact on transition metal chemistry and catalysis. By use of the calix[4]pyrrolato aluminate, [1]<sup>-</sup> , which features a square-planar Al<sup>III</sup> , we transfer this concept into the p-block and fully elucidate its mechanisms by experiment and theory. Complementary to transition metal-based MLC (aromatization upon substrate binding), substrate binding in [1]<sup>-</sup> occurs by dearomatization of the ligand. The aluminate trapps c  ...[more]

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