Spin-Controlled Binding of Carbon Dioxide by an Iron Center: Insights from Ultrafast Mid-Infrared Spectroscopy.

ABSTRACT: The influence of the spin on the mode of binding between carbon dioxide (CO₂ ) 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-CO₂ bonding patterns and determine their structure in situ by femtosecond mid-infrared spectroscopy. The formation of the nascent TM-CO₂ species according to [L₄ Fe^III (C₂ O₄ )]⁺ + hν → [L₄ Fe(CO₂ )]⁺ + CO₂ , with L₄ =cyclam, is evidenced by the coincident appearance of the characteristic asymmetric stretching absorption of the CO₂ -ligand between 1600 cm^-1

SUBMITTER: Straub S 

PROVIDER: S-EPMC7898313 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature