Spin delocalization

The EPR spectra of the related 1,2,4,6,3,5-thiatriazadiphosphinyl radicals (3.20) reveal a distinctly different electronic structure.The observed spectrum consists of a quintet of triplets consistent with coupling of the unpaired electron with two equivalent nitrogen atoms and two equivalent phosphorus atoms [Fig. 3.4(a)]. This interpretation was confirmed by the observation that the quintet collapses to a 1 2 1 triplet when the nitrogen atoms in the ring are 99% N-enriched [Fig 3.4(b)]. Thus the spin delocalization does not extend to the unique nitrogen atom in the phosphorus-containing system 3.20. 

Display spin density surfaces for all radicals. For which radical is the unpaired electron least delocalized from the radical center For which is it the most delocalized Is there any relationship between degree of puckering of the radical center and extent of spin delocalization ... 

First, try to draw resonance contributors for both ground state and triplet anthrone. Then display a spin density surface for the triplet state of anthrone. (Note that the spin density surface shows the location of both unpaired electrons, one of which may be in a 7t orbital and one of which may be in a o orbital.) Where are the two unpaired electrons Are they localized or delocalized Given that spin delocalization generally leads to stabilization, would you expect the triplet state of anthrone to be stable ... 

The orbital phase theory is applicable to the singlet diradicals [20]. The electron configuration of the singlet states of the cross- (TMM) and linear (BD) conjugate diradicals is shown in Scheme 9, where the mechanism of the delocalization of a and P spins between the radical centers through the double bond are separately illustrated by the arrows. The cyclic [-a-Tr-b-T -] interaction is readily seen to occur for the spin delocalizations. The p orbital a) in one radical center and the n orbital are occupied by a spins, and therefore, electron-donating orbitals. The p orbital (b) in the other radical center and the ii orbital are not occupied by a spins. 

Combines sensitivity of EPR and high resolution of NMR to probe ligand superhyperfine interactions For paramagnetic proteins enhanced chemical shift resolution, contact and dipolar shifts, spin delocalization, magnetic coupling from temperature dependence of shifts Identification of ligands coordinated to a metal centre... 

Several thiadiazole-fused organic radicals have been characterized by ESR spectroscopy, and significant spin delocalization can be seen from the hyperfine coupling constants (hfcc s) N (Table 5). 

Finally, similar stabilization has been observed for the homoallylic analogues 17, where the preferred conformation is one in which the C—M bond eclipses the jr-system containing the unpaired spin53. Clearly, this mechanism of spin delocalization is of general nature. 

Since most of the carbenes 1 have triplet ground states, ESR spectroscopy allows to see the unpaired electrons and determine the local symmetry at the carbene center and the amount of spin delocalization.13-18 Most of the ESR spectra of carbenes reported in the literature have been recorded in organic glasses or powder samples at temperatures between 4 and 77 K. Many carbenes are slightly colored and exhibit characteristic absorptions extending to the visible region of the spectrum. UV/vis spectroscopy not only provides information on the excited states of carbenes, which in many cases are the reactive species during precursor photolyses, but also links low temperature spectroscopy to LFP in solution at room temperature. 

When considering the stability of spin-delocalized radicals the use of isodesmic reaction Eq. 1 presents one further problem, which can be illustrated using the 1-methyl allyl radical 24. The description of this radical through resonance structures 24a and 24b indicates that 24 may formally be considered to either be a methyl-substituted allyl radical or a methylvinyl-substituted methyl radical. While this discussion is rather pointless for a delocalized, resonance-stabilized radical such as 24, there are indeed two options for the localized closed shell reference compound. When selecting 1-butene (25) as the closed shell parent, C - H abstraction at the C3 position leads to 24 with a radical stabilization energy of - 91.3 kj/mol, while C - H abstraction from the Cl position of trans-2-butene (26) generates the same radical with a RSE value of - 79.5 kj/mol (Scheme 6). The difference between these two values (12 kj/mol) reflects nothing else but the stability difference of the two parents 25 and 26. 

Esr spectroscopy has been used extensively in connection with the problem of radical stabilization. Two properties of the radicals are analysed to obtain information on their stability spin-density distribution and lifetime. The former has a solid physical basis in hyperfine splitting and the universally accepted hypothesis that spin delocalization accords stability to a free radical (for a discussion, see Walton, 1984). The more the unpaired spin density is delocalized, the higher is, supposedly, the stability of the radical. This argument, as we shall see, is mainly used on a qualitative basis (see. 

Spin-density distributions are inherent features of free radicals. Esr experiments take place when the radical is in its electronic ground state and the measurement of the spin distribution constitutes only a minute perturbation of the system. This feature and the fact that esr hyperfine splitting can be measured with high precision makes the esr method ideally suited for the study of substituent effects. Therefore, if spin delocalization is accepted as a measure of stabilization, the data in Table 6 provide quantitative information. However, these are percentage values and not energies of stabiliza-... 

In [16e-h] it appears that, since the spin delocalization is considerable, the radicals must be kinetically less stable at sites other than the original radical centre where there is no steric protection. Therefore, it was difficult to obtain samples that contain satisfactory spin concentrations. In [16j] and [16k], by contrast, the spin distribution seems not to be extensive and so the kinetic stability of the radical centres must be well protected. 

A typical example of steric control over spin delocalization has been described for the cation-radical of 3,4-bis(thioisopropyl)-2,5-dimethyl-l-phenylpyrrole (Domingo et al. 2001). Scheme 3.15 depicts this sitnation. In this cation-radical, one thioisopropyl group is almost coplanar with the pyrrole ring, whereas the other one occupies an orthogonal position. Accordingly, the ESR spectra established an eqnilibrinm between the symmetrical and asymmetrical conformations of the cation-radical. This equi-librinm is shifted toward the asymmetrical form at low temperatmes. The main feature of the equilibrium is the widening of spin delocalization, which includes not only the pyrrole ring but also one donor sulfur atom at the expense of the other sulfur atom. The steric control predetermines the discrimination of the other sulfur atom in the spin-delocalization process. 

The cation-radical of permethyldithia[6]radialene provides one, even more pertinent, example of the steric control over spin delocalization (Gleiter et al. 1996). As described, the unpaired electron is delocalized only in one half of this cation-radical, namely, within the limits of the 2,3-dithiatetramethyl-butadiene unit. Owing to the steric demand of the isopropilidene groups, two of the four methylene groups are twisted, whereas the other two are coplanar (see Scheme 3.16). It seems... 

In a similar manner, p-bis(9-anthryl) phenylene gives a mono(anion-radical) or a mono(cation-radical) under reductive or oxidative conditions with spin delocalization around the whole molecular framework. In the case of m-bis(9-anthryl) phenylene, reduction or oxidation leads to the formation of dianion or dication-diradicals. Based on ESR experiments at cryogenic temperatures (6.5-85 K), these species contain two separated ion-radical moieties. They have parallel aligmnent of their spins (Tukada 1994). The work gives clear experimental evidence for the so-called ferromagnetic interaction between these ion-radical substituents. In some cases, release of the electron depends on temperature. See, for example, the anion-radical shown in Scheme 3.63. 

The second example depicted in Scheme 3.64 is the trioxotriphenylamine cation-radical. Kuratsu et al. (2005) compared structures of the cation-radical and its neutral counterpart. The neutral compound has a shallow bowl structure, whereas the cation-radical has a planar structure. In the latter, spin delocalization embraces a whole molecular contour, involving the oxygen atoms. This contribntes to the cation-radical stability. (The solid species is easily formed after oxidation of the neutral parent compound with tris(p-bromophenyl)aminiumyl hexafluorophosphate in methylene... 

The fonrth example in Scheme 3.64 puts forward the most stable cation-radical of hexaaza-octadecahydrocoronene (Miller et al. 1990). This cation-radical is characterized by effective spin delocalization with the participation of all its six nitrogen atoms. Interestingly, the parent neutral compound gives not only the cation-radical, but also the dication, tri(cation)-radical, and even tetracation. All of these cationic forms are stable and their crystal structures were described. 

Spin Delocalization in Ion-Radicals Derived prom Molecules OP Increased Dimensionality... 

Henning et al. (2006) used spectroelectrochemical and DFT methods to follow conformational transition of 3,6-diphenyl-l,2-dithiin by one-electron oxidation. The primary cation-radical is flattened partially. This cation-radical was fixed at 223 K. Heating up to 293 K provided this cation-radical with an additional energy. It resulted in the formation of an entirely planar structure with complete spin delocalization within the molecular framework. The transition is depicted in Scheme 6.22. 

---