DMSO oxygen atom

In the luminescence reaction of firefly luciferin (Fig. 1.12), one oxygen atom of the product CO2 is derived from the molecular oxygen while the other originates from the carboxyl group of luciferin. In the chemiluminescence reaction of an analogue of firefly luciferin in DMSO in the presence of a base, the analysis of the product CO2 has supported the dioxetanone pathway (White et al., 1975). 

The last point has been studied more quantitatively for the electrolyte LiOjCCH Fy (x+y=3) / DMSO [97,105], Semiempirical quantum-mechanical calculations with the help of MOP AC [143] show that the mean electron density at the oxygen atoms q(0) decreases for these acetates by about 0.1 unit with increasing fluorine content of the anion [97]. As a consequence ... 

Figure 4. Linear correlation of In vs. mean charge density of oxygen atoms, < (0)MNDO, for LiCLCCHx Fy pc + y = 3/ DMSO. ...

Obviously, this shift implies the self-association of DMSO. Further frequency shifts to even lower wave numbers (1050-1000 cm " ) are observed in both aprotic polar and protic solvents. In aprotic solvents such as acetonitrile and nitromethane, the association probably takes place between the S—O bond of DMSO and the —C=N or the —NOz group in the molecules by dipole-dipole interaction as shown in Scheme 331,32. Moreover, the stretching frequency for the S—O bond shifts to 1051 cm 1 in CHC13 and to 1010-1000 cm -1 in the presence of phenol in benzene or in aqueous solution33. These large frequency shifts are explained by the formation of hydrogen bonds between the oxygen atom in the S—O bond and the proton in the solvents. Thus, it has been... 

The sites for complex formation in DMSO with inorganic salts depend remarkably on the nature of the metals involved in the salts. The alkali or alkali earth metallic salts form a complex with the oxygen atom in DMSO while Pd(II) or Pt(II) associates strongly at the sulphur atom. The IR frequency of the S—O bond of DMSO shifts to even lower wave numbers when associated with such metal cations as Li+, Na+ or Ca+ +34. On the other hand, in the case of Pd(II) or Pt(II), the S—O frequency appears at higher wave numbers, at around llOO-llAOcm 135. These different shifts for the S—O frequency afford a convenient diagnosis to determine whether the cation associates with the oxygen or the sulphur atom in DMSO. 

Diverse series of diphenyl sulphoxide (DPSO) complexes of Mn(II), Fe(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ca(II), Al(II) and Mg(II) with various large anions have been reported187-191. The complexes have the general formula M(DPSO)6(Anion) where M is the metal cation. The reflection spectra in the visible and near-IR region indicate an octahedral configuration around the metal ion surrounded by the DPSO molecules. Comparison with the spectra of DMSO complexes shows that they have almost identical structures. IR spectra indicate that the oxygen atom in the sulphinyl group is the donor atom in all these complexes. 

The infrared174-176 and X-ray175,193,194 studies demonstrate that though DMSO generally associates with metal cations through its oxygen atom, the donation by the sulphur atom is favoured for some cations, such as Pt(II) and Pd(II). However, Wayland... 

This oxidation of DMSO is catalyzed by Ag+ cations. Kinetic and infrared spec-trometric evidence fits a mechanism where DMSO coordinates rapidly with Ag+ through its oxygen atom. The oxidation of this complex by Ce4 + then constitutes the slow step. The Ag2+ adduct would then undergo an intramolecular electron transfer in a fast step resulting in the oxidation of DMSO. 

H). As shown, a disordered structural model was obtained for the guest. The model comprises two mirror-related guest molecules. The oxygen atom and the proximal methyl C-atom are practically overlapping the same atomic positions in both orientations. However, the sulphur atomic positions do not average in the X-ray data and show a nearly 50/50 occupancy. As indicated by the comparison of the respective bond distances and intra-associate contact distances of the DMSO molecule (Table 17), the effect of disorder is serious (e.g. the S=0 distances appear abnormally short in the 20 DMSO instance). This precludes the possibility of assessing interaction between the O atom of the carboxyl and a methyl of dimethyl sulfoxide. 

In the case of the DMSO reductase family, as pointed out above, the metal centre is bound to two molecules of the cofactor. DMSO reductase itself catalyses the reduction of dimethylsulfoxide to dimethylsulfide with incorporation of the oxygen atom of DMSO into water. The active site of the oxidized enzyme is an L2MoVI0(0-Ser) centre, which, upon reduction, loses the M=0 ligand to give a L2MoIV(0-Ser) centre. In the catalytic... 

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