Cis-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2, the poor relative between cis and trans tautomers. A theoretical study of the gas-phase Fe L3-edge and C and O K-edge XAS of trans-/cis-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2. Issue 43 (27th October 2021)

• Record Type: Journal Article
• Authors: Carlotto, Silvia; Casella, Girolamo; Sambi, Mauro; Casarin, Maurizio
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 43(2021)
• Page Start: 24661
• Page End: 24668
• Publication Date: 2021-10-27
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp04105c
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The relative stability of trans -[(η 5 -C5 H5 )Fe(η 1 -CO)(μ-CO)]2 ( trans -I ) and cis -I tautomers in a vacuum and in solvents with different dielectric constants ( ε ) has been investigated by exploiting density functional theory (DFT). Abstract : The relative stability of trans -[(η 5 -C5 H5 )Fe(η 1 -CO)(μ-CO)]2 ( trans -I ) and cis -I tautomers in a vacuum and in solvents with different dielectric constants ( ε ) has been investigated by exploiting density functional theory (DFT). Theoretical results indicate that, in agreement with experimental evidence, trans -I is more stable than cis -I in a vacuum (∼1.5 kcal mol −1 ; ε = 1), while the opposite is true in media with ε > 7. Differently from solution, DFT outcomes pertaining to the vapor-phase cis -I ⇆ trans -I equilibrium at T = 368 K, the temperature at which the Fe L2, 3 -edges and the C and O K-edge X-ray absorption spectroscopy (XAS) data of I have been recorded, ultimately indicate the trans -I predominance (∼93%). Compositions, oscillator strengths ( f ) and excitation energy ( EE ) values of cis -I transitions substantially mirror those of trans -I ; nevertheless, the weighted cis -I f ( EE ) distributions negligibly contribute to the diverse simulated XA spectra of I .