Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 23, Issue 43, Pages 24661-24668Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cp04105c
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Funding
- University of Padova [CARL-SID17 BIRD2017-UNIPD]
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Using density functional theory, the relative stability of two tautomers in solvents with different dielectric constants was studied. It was found that trans-I is more stable in a vacuum, while cis-I is more stable in media with epsilon > 7. Experimental data at 368K also indicate trans-I predominance.
The relative stability of trans-[(eta(5)-C5H5)Fe(eta(1)-CO)(mu-CO)](2) (trans-I) and cis-I tautomers in a vacuum and in solvents with different dielectric constants (epsilon) 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 (similar to 1.5 kcal mol(-1); epsilon = 1), while the opposite is true in media with epsilon > 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 L-2,L-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 (similar to 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.
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