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Interactions of ferrocenes with protic and halocarbon solvents: predominance of the intermolecular charge transfer to solvent

Content Provider	Springer Nature Link
Author	Rabie, Usama M.
Copyright Year	2012
Abstract	Electronic absorption spectra of acetylferrocene, 1,1′-dimethylferrocene, and benzoylferrocene in pure organic polar and non-polar solvents, in pure halocarbon solvents, and in several hexane–halocarbon solvent mixtures were recorded. The electronic spectra have shown that the investigated ferrocenes have several intramolecular electronic transitions of the types π–π, n–π, and d–d. On using protic solvents (HA), each of the ferrocenes (Fc) acquires a proton from the applied solvent, whereas a complex with the formula [FcH]$^{+}$[A]$^{−}$ is formed. Formation constants and the free energy change of these complexes have been determined and discussed. However, on using halocarbon solvents, each of the ferrocenes performed an intermolecular charge-transfer-to-solvent transition which was characterized by the appearance of a new absorption spectral band(s) for each ferrocene–halocarbon solvent interaction. Formation constants and molar absorption coefficients of these interactions have been determined and discussed. The study indicated that the observed different electronic transitions were dependent on the nature of the substituent group(s) attached to the cyclopentadienyl moieties of the studied ferrocenes.Interaction of ferrocenes with halocarbon solvents results in weak complexes via an intermolecular (contact) charge transfer to solvent (CTTS). Thus, the spectra of each of the studied ferrocenes in hexane–chlorinated mixed solvent show that on increasing the concentration of the chlorinated solvent and decreasing the concentration of hexane, the band observed when using hexane only, which is assigned an n–π electronic intra-transitions (MLCT), gradually diminishes, while another new band attributed to CTTS grows with increase of its intensity. Consequently, it has been confirmed that the intermolecular CTTS is energetically more favorable than its simultaneous competitor intramolecular MLCT within the ferrocene moieties.
Starting Page	357
Ending Page	366
Page Count	10
File Format	PDF
ISSN	1735207X
Journal	Journal of the Iranian Chemical Society
Volume Number	10
Issue Number	2
e-ISSN	17352428
Language	English
Publisher	Springer-Verlag
Publisher Date	2012-09-18
Publisher Place	Berlin, Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Analytical Chemistry Physical Chemistry Halocarbon solvents Ferrocenes Biochemistry Intra- and intermolecular transitions Inorganic Chemistry Charge transfer Electronic spectra Organic Chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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