Studies on the interaction of peroxy radicals with transition metals complexes

„Aus der Luft gegriffen“ wird molekularer Sauerstoff bei rhodiumvermittelten Umwandlungen zu Wasserstoffperoxid, Bis(trimethylsilyl)peroxid und Methylhydroperoxid. Intermediäre η1‐Hydroperoxo‐, η1‐Silylperoxo‐ und η1‐Methylperoxo‐Verbindungen konnten isoliert werden. Ein weiterer η1‐Methylperoxo‐Komplex (siehe Bild) und ein η1‐Hydroperoxo‐Komplex wurden durch Röntgenstrukturanalyse charakterisiert.

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Rhodiumvermittelte Bildung von Peroxiden aus Disauerstoff: Isolierung von Hydroperoxo‐, Silylperoxo‐ und Methylperoxo‐Intermediaten

Ahijado

Braun

Noveski

et al. 2005

Angewandte Chemie

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Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

et al. 2019

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Switchable polymerization provides the opportunity to regulate polymer sequence and structure in ao ne-pot process from mixtures of monomers.Herein we report the use of O 2 as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)Co III À R[ Salen = N,N'-bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediamine;R = alkyl] to the ring-opening copolymerization (ROCOP) of CO 2 /epoxides. Critical to this process is unprecedented monooxygen insertion into the CoÀCb ond, as rationalized by DFT calculations, leading to the formation of (Salen)Co III À O À Ra sa na ctive species to initiate ROCOP.D iblock poly(vinyl acetate)-bpolycarbonate could be obtained by ROCOP of CO 2 /epoxides with preactivation of (Salen)Co end-capped poly(vinyl acetate). Furthermore,ap oly(vinyl acetate)-b-poly(methyl acrylate)-b-polycarbonate triblock copolymer was successfully synthesized by a( Salen)cobalt-mediated sequential polymerization with an O 2 -triggered switchinaone-pot process.

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Rhodium‐Mediated Formation of Peroxides from Dioxygen: Isolation of Hydroperoxo, Silylperoxo, and Methylperoxo Intermediates

et al. 2005

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Studies on the interaction of peroxy radicals with transition metals complexes

Cited by 6 publications

References 29 publications

Rhodiumvermittelte Bildung von Peroxiden aus Disauerstoff: Isolierung von Hydroperoxo‐, Silylperoxo‐ und Methylperoxo‐Intermediaten

Rhodiumvermittelte Bildung von Peroxiden aus Disauerstoff: Isolierung von Hydroperoxo‐, Silylperoxo‐ und Methylperoxo‐Intermediaten

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

Rhodium‐Mediated Formation of Peroxides from Dioxygen: Isolation of Hydroperoxo, Silylperoxo, and Methylperoxo Intermediates

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Studies on the interaction of peroxy radicals with transition metals complexes

Cited by 6 publications

References 29 publications

Rhodiumvermittelte Bildung von Peroxiden aus Disauerstoff: Isolierung von Hydroperoxo‐, Silylperoxo‐ und Methylperoxo‐Intermediaten

Rhodiumvermittelte Bildung von Peroxiden aus Disauerstoff: Isolierung von Hydroperoxo‐, Silylperoxo‐ und Methylperoxo‐Intermediaten

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Rhodium‐Mediated Formation of Peroxides from Dioxygen: Isolation of Hydroperoxo, Silylperoxo, and Methylperoxo Intermediates

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Product

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Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures