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Articles by Nils Ansmann
Silicon‐Catalyzed Depolymerization of Polyethers: Pushing Scope, Practicability and Mechanistic Understanding
Introduction Metathesis of C(sp3)−X bonds gained increasing attention in past decades but is still much underdeveloped compared to metathesis reactions of other bonds.1 As commonly employed C−X bond activations by oxidative addition encounter obstacles from high reaction barriers and side reactions like β-hydride elimination, Lewis acid catalysis emerged as a powerful alternative for this type of transformation.2 Pioneering work by Enthaler et al.
Neutral and Anionic Square Planar Palladium(0) Complexes Stabilized by a Silicon Z‐Type Ligand
The involvement of anionic Pd(0) intermediates in cross-coupling reactions like the Heck, Suzuki, Stille or Buchwald–Hartwig reactions is widely accepted in organometallic catalysis.1 While increased yields were often noticed upon the addition of halide salts, corresponding intermediates were never isolated, and the molecular explanation of the effect remained debated.2 In pioneering work, Amatore and Jutand used electrochemistry and 31P NMR spectroscopy to justify the rate acceleration in...
Silicon Catalyzed C−O Bond Ring Closing Metathesis of Polyethers
Abstract The Lewis superacid bis(perchlorocatecholato)silane is applied in the selective catalytic C−O ring-closing metathesis of challenging oligo- and polyethers, enabling upcycling of polyethylene glycol. Based on detailed investigations of the reaction mechanism by DFT calculations, an improved second-generation silicon-based Lewis superacid is developed.
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