Details

Autor(en) / Beteiligte

• Gupta, Navneet K.
• Pashigreva, Anastasia
• Pidko, Evgeny A.
• Hensen, Emiel J. M.
• Mleczko, Leslaw
• Roggan, Stefan
• Ember, Erika E.
• Lercher, Johannes A.

Titel

Bent Carbon Surface Moieties as Active Sites on Carbon Catalysts for Phosgene Synthesis

Ist Teil von

• Angewandte Chemie (International ed.), 2016-01, Vol.55 (5), p.1728-1732

Auflage

International ed. in English

Ort / Verlag

Germany: Blackwell Publishing Ltd

Erscheinungsjahr

2016

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Active sites in carbon‐catalyzed phosgene synthesis from gaseous CO and Cl2 have been identified using C60 fullerene as a model catalyst. The carbon atoms distorted from sp2 coordination in non‐planar carbon units are concluded to generate active Cl2. Experiments and density functional theory calculations indicate the formation of a surface‐bound [C60⋅⋅⋅Cl2] chlorine species with radical character as key intermediate during phosgene formation. It reacts rapidly with physisorbed CO in a two‐step Eley–Rideal‐type mechanism. Active sites and reactive intermediates: Experiments and DFT calculations provide insight into the mechanism of carbon‐catalyzed Cl2 activation and COCl2 formation. The structural resemblance between the C60 fullerene and active carbon catalysts showed that carbon sites distorted from sp2 coordination in non‐planar units are the active sites, catalyzing the process via an active [C60⋅⋅⋅Cl2] complex.