Back to Search
Start Over
Spin-Controlled Binding of Carbon Dioxide by an Iron Center: Insights from Ultrafast Mid-Infrared Spectroscopy.
- Source :
-
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 Feb 01; Vol. 60 (5), pp. 2519-2525. Date of Electronic Publication: 2020 Nov 27. - Publication Year :
- 2021
-
Abstract
- The influence of the spin on the mode of binding between carbon dioxide (CO <subscript>2</subscript> ) and a transition-metal (TM) center is an entirely open question. Herein, we use an iron(III) oxalato complex with nearly vanishing doublet-sextet gap, and its ultrafast photolysis, to generate TM-CO <subscript>2</subscript> bonding patterns and determine their structure in situ by femtosecond mid-infrared spectroscopy. The formation of the nascent TM-CO <subscript>2</subscript> species according to [L <subscript>4</subscript> Fe <superscript>III</superscript> (C <subscript>2</subscript> O <subscript>4</subscript> )] <superscript>+</superscript> + hν → [L <subscript>4</subscript> Fe(CO <subscript>2</subscript> )] <superscript>+</superscript> + CO <subscript>2</subscript> , with L <subscript>4</subscript> =cyclam, is evidenced by the coincident appearance of the characteristic asymmetric stretching absorption of the CO <subscript>2</subscript> -ligand between 1600 cm <superscript>-1</superscript> and 1800 cm <superscript>-1</superscript> and that of the free CO <subscript>2</subscript> -co-fragment near 2337 cm <superscript>-1</superscript> . On the high-spin surface (S=5/2), the product complex features a bent carbon dioxide radical anion ligand that is O-"end-on"-bound to the metal. In contrast, on the intermediate-spin and low-spin surfaces, the product exhibits a "side-on"-bound, bent carbon dioxide ligand that has either a partial open-shell (for S=3/2) or fully closed-shell character (for S=1/2).<br /> (© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1521-3773
- Volume :
- 60
- Issue :
- 5
- Database :
- MEDLINE
- Journal :
- Angewandte Chemie (International ed. in English)
- Publication Type :
- Academic Journal
- Accession number :
- 33022879
- Full Text :
- https://doi.org/10.1002/anie.202012739