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

Autor:	Silvia Carlotto, Mauro Sambi, Girolamo Casella, Maurizio Casarin
Rok vydání:	2021
Předmět:	X-ray absorption spectroscopy Materials science K-edge Absorption spectroscopy General Physics and Astronomy Physical chemistry Density functional theory Dielectric Physical and Theoretical Chemistry Tautomer Spectral line Cis–trans isomerism
Zdroj:	Physical Chemistry Chemical Physics. 23:24661-24668
ISSN:	1463-9084 1463-9076
DOI:	10.1039/d1cp04105c
Popis:	The relative stability of trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 (trans-I) and cis-I tautomers in a vacuum and in solvents with different dielectric constants (e) 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; e = 1), while the opposite is true in media with e > 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-If(EE) distributions negligibly contribute to the diverse simulated XA spectra of I.
Databáze:	OpenAIRE
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