Details

Autor(en) / Beteiligte

• Straub, Steffen
• Brünker, Paul
• Lindner, Jörg
• Vöhringer, Peter

Titel

An Iron Complex with a Bent, O‐Coordinated CO2 Ligand Discovered by Femtosecond Mid‐Infrared Spectroscopy

Ist Teil von

• Angewandte Chemie International Edition, 2018-04, Vol.57 (18), p.5000-5005

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2018

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The activation of carbon dioxide by transition metals is widely recognized as a key step for utilizing this greenhouse gas as a renewable feedstock for the sustainable production of fine chemicals. However, the dynamics of CO2 binding and unbinding to and from the ligand sphere of a metal have never been observed in the time domain. The ferrioxalate anion is used in aqueous solution as a unique model system for these dynamics and femtosecond UV‐pump mid‐infrared‐probe spectroscopy is applied to explore its photoinduced primary processes in a time‐resolved fashion. Following optical excitation, a neutral CO2 molecule is expelled from the complex within about 500 fs to generate a highly intriguing pentacoordinate ferrous dioxalate that carries a bent carbon dioxide radical anion ligand, that is, a reductively activated form of CO2, which is end‐on‐coordinated to the metal center by one of its two oxygen atoms. Optical excitation of ferrioxalate leads to an ultrafast cleavage of a neutral carbon dioxide molecule. Thereby, a ferrous dioxalate is generated bearing a bent carbon dioxide ligand in an O‐“end‐on” fashion.