Stereospecific Carbene Polymerization with Oxygenated Rh(diene) Species

Stereospecific Carbene Polymerization with Oxygenated Rh(diene) Species

Breath‐taking activation: Stereoregular carbene polymerization proceeds via cationic [(allyl)RhIII–polymeryl]+ species. These are most efficiently generated by oxygenation of the [(diene)RhI] precatalysts, which involves an unusual rearrangement of 2‐rhodaoxetane intermediates. This discovery gives...

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Veröffentlicht in:Angewandte Chemie International Edition 2012-05, Vol.51 (21), p.5157-5161
Hauptverfasser: Walters, Annemarie J. C., Troeppner, Oliver, Ivanović-Burmazović, Ivana, Tejel, Cristina, del Río, M. Pilar, Reek, Joost N. H., de Bruin, Bas
Format: Artikel
Sprache:eng
Schlagworte:
Activation
Aluminum base alloys
Carbenes
Cationic
diazo compounds
Mass Spectrometry
oxidation
Oxygen - chemistry
Oxygenated
Oxygenation
Polymerization
Polymers - chemistry
Reaction mechanisms
rhodium
Rhodium - chemistry
Stereoisomerism
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Zusammenfassung:Breath‐taking activation: Stereoregular carbene polymerization proceeds via cationic [(allyl)RhIII–polymeryl]+ species. These are most efficiently generated by oxygenation of the [(diene)RhI] precatalysts, which involves an unusual rearrangement of 2‐rhodaoxetane intermediates. This discovery gives detailed insight in the reaction mechanism.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201200069