Sulfur atoms, electronic states

Both CSs and CSs were also successfully generated by the fragmentation of ionized 4,5-dioxo-2-thioxo-l,3-dithione (65) and 2-thioxo-l,3-dithiole (66) (90JA3750). Tire three sulfur atoms in the anion and cation radicals were chemically equivalent, suggesting that they take the D h (or C2u) form (67 or 68). On the other hand, under similar conditions, 3-thioxo-1,2-dithiole (69) yielded two isomeric cation radicals the (or 2 ) form and the carbon disulfide 5-sulfide form (70). Ab initio calculations on three electronic states of CS3 at the 6-31G -l-ZPVE level indicated that the C21, form (68) was more stable than the carbon disulfide 5-sulfide form (70) in the neutral (both singlet and triplet states) and the anion radical states, but 68 was less stable than 70 in the radical cation state. 

Both the sulfone and the sulfoxide groups are characteristically electrophilic based on the increasing electropositivity of the sulfur atom in proportion to its oxidation state. Therefore, the nucleophilicity of these groups can be discussed only in terms of the nucleophilicity of either the trivalent sulfur atom, still having a pair of nonbonding electrons, or the oxygen atom in the sulfoxides. 

There will exist an equilibrium between the two states. If the ener between the two states, E, is of the order of kT, then the relative populations of the two states will vary with the temperature of the sample. In the Fe(III) dithiocarbamate series of complexes, [FeCRiRgdtcla], AE can be varied by suitable choice of substituents Ri and Rj. Although these are well removed from the FeSg molecular core, they can appreciably affect the electronic parameters of the central iron atom and of the surrounding crystal field of the sulfur atom by way of the conjugated system of the ligand (237). The results of the spin crossover are reflected in magnetic susceptibility data. 

The effect shown in Fig. 9 is a result of the bond-bond interaction which is a characteristic feature for chains and rings of two-valent chalcogen atoms. It can also be recognized from the relatively large bond interaction force constants fir of such compounds. The stretching force constants /r(SS) of polysulfur compounds depend on the SS bond distances as shown in Fig. 10. The data used in this figure include several excited electronic states of the S2 molecule as well as the disulfide anion and a number of sulfur homocycles [77]. 

Write the shorthand electron configuration and draw the ground-state orbital energy level diagram for the valence electrons in a sulfur atom. 

C08-0111. None of the four proposed electron energy diagrams shown below describes the ground state of a sulfur atom. For each, state the reason why it is not correct ... 

From the good correspondence between the calculated and experimental --values and hfs s, one may conclude that the MO s, calculated with these values for the empirical parameters, give a fair description for the ground state of Cu(Et2C fc)2. The results of the calculation show that the bonding in Cu(Et2C fc)2 is largely covalent, with overlap populations between copper and sulfur atoms of 0.22 electron unit. 

The S02 molecule has unshared pairs of electrons on both the sulfur and oxygen atoms. As a result, it forms numerous complexes with transitions metals in which it is known to attach in several ways. These include bonding through the sulfur atom, through an oxygen atom, by both oxygen atoms, and various bridging schemes. In most cases, the complexes involve soft metals in low oxidation states. Another important reaction of sulfur dioxide is known as the insertion reaction, in which it is placed... 

XAS data comprises both absorption edge structure and extended x-ray absorption fine structure (EXAFS). The application of XAS to systems of chemical interest has been well reviewed (4 5). Briefly, the structure superimposed on the x-ray absorption edge results from the excitation of core-electrons into high-lying vacant orbitals (, ] ) and into continuum states (8 9). The shape and intensity of the edge structure can frequently be used to determine information about the symmetry of the absorbing site. For example, the ls+3d transition in first-row transition metals is dipole forbidden in a centrosymmetric environment. In a non-centrosymmetric environment the admixture of 3d and 4p orbitals can give intensity to this transition. This has been observed, for example, in a study of the iron-sulfur protein rubredoxin, where the iron is tetrahedrally coordinated to four sulfur atoms (6). 

When the BETS donor replaces the BEDT-TTF electron donor molecule during the electrocrystallization process, crystals of KL-(BETS)2Ag(CF3)4(TCE) have been prepared [29] and structurally characterized. Replacement of the inner sulfur atoms of BEDT-TTF with selenium results in a slight expansion of the unit cell and prevents the stabilization of a superconducting state above 1.2 K. Disorder in one of the BETS ethylene endgroups has been offered as a possible explanation. 

We have already mentioned a very strong dyadic association in the formally d5 cobalt complexes such as [Cp Co(dddt)]+ which dimerizes in the solid state to a fully diamagnetic dicationic dyad (Fig. 6a). It represents the extreme situation where the two radicals form a true 2e bond, with the sulfur atom of one dithiolene ligand entering the coordination sphere of the other metal. It should be considered as the consequence of the electron deficiency of these cationic [CpCo(dt)]+ 15-electron complexes. 

As with SO + 03, discussed above, it is believed that sulfur monoxide reacts with ground-state O atoms to form S02 in either the 3Bj or B2 electronic states, although the A2 and Bj may also contribute [24, 28, 29], Standard third-order chemiluminescence reaction mechanisms and kinetics are thought to apply ... 

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