Thiophenols ionization

The spectrum shown in Figure 2(c) is that of CpFe(CO)2(SPh). This photoelectron spectrum is more complicated due to the presence of the additional ionizations from the Ph jt and S 3p lone pair. The electronic structure of CpFe(CO)2(SPh) can be considered as the combination of the [CpFe(CO)2]+ and [SPh] fragments, and the photoelectron spectrum of the CpFe(CO)2H and thiophenol (HSPh, shown in Figure 2d) can be used to model the ionizations of these fragments. The three lowest energy ionizations of thiophenol correspond to a mixture of sulfur lone pair and aryl jt character, with the lowest energy (highest occupied molecular orbitals (HOMO)) ionization attributed to the orbital with the most sulfur lone pair character. For CpFe(CO)2(SPh),... 

This concept has been proofed for other compounds than phenols such as thiophenols/ selenols and also secondary aromatic amines. And indeed, an analogous reaction behavior has been found. FET ionization resulted in two products metastable radical cations and radicals corresponding to the dissociative cation structure. Furthermore, the concept is also working for compounds where instead of protons, another leaving group has been used as symbolized for the following... 

Methylation is rarely of quantitative importance in the metabolism of xenobiotics. The methyl group is transferred from the nucleotide S-adenosyl-L-methionine (SAM) by means of a methyltransferase. The functional groups that undergo methylation include primary, secondary and tertiary amines, pyridines, phenols, catechols, thiophenols. The aza-heterocycle pyridine is metabolized to the A-methylpyridin-ium ion, which is more toxic than pyridine itself (Figure 33.18). The binding properties of the ionized metabolite are disturbed by the loss of its hydrophobic feature, resulting from the polarity inversion. 

This type of interaction is possible with thiophenol and anthracene whose ionization potentials are, respectively, 8.3 and 7.5 eV [345], but less probable with ethyl- and butylamine which have ionization potentials close to that of pyridine (respectively, 9.19 and 8.79) [345]. Amines and thiophenol can also interact with the radicals formed in the polymer according to... 

Discussion about the electronic structures of thiophenol has been revived by the elucidation of the photoelectron (p.e.) spectra. - Using ir-molecular orbitals based on the validity of Koopmans theorem, Bock et al/ have nicely visualized the different behaviour of (6) and (7) on ionization. In Figure 1 the qualitative MO schemes are compared with the corresponding... 

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