In:
Physical Chemistry Chemical Physics, Royal Society of Chemistry (RSC), Vol. 23, No. 43 ( 2021), p. 24661-24668
Abstract:
The relative stability of trans -[(η 5 -C 5 H 5 )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 L 2,3 -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.
Type of Medium:
Online Resource
ISSN:
1463-9076
,
1463-9084
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2021
detail.hit.zdb_id:
1476283-3
detail.hit.zdb_id:
1476244-4
detail.hit.zdb_id:
1460656-2
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