Hyperfine splittings

Oxidation of azole anions can give neutral azole radicals which could, in principle, be tt (139) or a- (140) in nature. ESR spectra indicate structure (141 hyperfine splittings in G) for imidazolyl radicals, but both tt- and cr-character have been observed for pyrazolyl radicals. Tetrazolyl radicals (142 4 143) are also well known (79AHC(25)205). Oxidation of 2,4,5-triarylimidazole anions with bromine gives l,l -diimidazolyls (144) which are in equilibrium with the dissociated free radical (145) (70AHQ 12)103). 

A second type of structural information can be deduced from the hyperfine splitting in EPR spectra. The origin of this splitting is closely related to the factors that cause spin-spin splitting in proton NMR spectra. Certain nuclei have a magnetic moment. Those which are of particular interest in organic chemistry include H, " N, F, and P. 

The " N nucleus (/ = 1, 99%) has a moderately large magnetic moment and hyperfine splittings from this nucleus are a distinctive feature of the EPR spectra of chalcogen-nitrogen radicals. A-Arylthio-2,4,6-triphenylanilino radicals (3.16) are exceptionally persistent and oxygen-insensitive m solution. They exhibit a characteristic 1 1 1... 

In this exercise, we will predict the isotropic hyperfine splitting in HNCN radical at a... 

Tlie following summarizes g-values and hyperfine splitting values by ( h) and by ( 33s) in natural abundance for the representative 1,2-dithiete radical cations. 

The spin adducts of free radicals and MNP or DMPO were observed by means of an ESR spectrometer. The data of hyperfine splitting constants were compiled in Tables 9 and 10 [40-42,44,45]. ESR studies on the initial free radicals revealed that the monoalkylamino radical RHN-, dialkylamino radical R2N-, and aminomethyl radical -CH2N< or aminoethylidene radical >N( CHCH3) were obtained from the corresponding primary, secondary, and cyclic tertiary amine. In case of a tertiary diamine such as TMEDA, formation of... 

Table 9 Hyperfine Splitting Constants of Spin Adduct Formed APS/Amine/MNP or DMPO System ...

Tabie 10 Hyperfine Splitting Constants of Spin Adducts Obtained from APS/Amine/MNP Systems... 

System Radical trapped by MNP Hyperfine splitting constant (0.1 mT) ap ap a," ... 

A good correlation with ordinary Hammett a values was based on 16 well-behaved substituents, and p-SOMe conformed well to this. Various other substituents showed deviations which were attributed to enhanced + R effects. These included p-SPh and this was explained in terms of 7t(pd) bonding, which was thus taken to play no part in the effect of p-SOMe on the methyl hyperfine splitting. More recently several 4-substituted benzyl radicals of the type RSO C6H4CH2 (n — 0,1 or 2 R = Me, Ph, Tol, COMe or OMe) have been examined by ESR spectroscopy249. The ability to delocalize spin density onto the substituent decreases in general as n increases and the effect of R depends on the oxidation state of sulfur. These authors have devised a new scale of substituent effects (sigma dot... 

TABLE 3. Hyperfine splitting constants (gauss) of some sulfur-cpntaining aromatic radical anions obtained in 1,2-dimethoxyethane with K metal as the reductant at — 80 °C... 

TABLE 4. Hyperfine splitting constants (gauss) of thioxanthone S-(mono or dijoxide radical anions as free or tight contact ion-pair ... 

The ESR spectra of a large variety of sulfonyl radicals have been obtained photolytically in liquid phase over a wide range of temperature. Some selected data are summarized in Table 2. The magnitudes of hyperfine splittings and the observations of line broadening resulting from restricted rotation about the C—S bond have been used successfully in conjunction with INDO SCF MO calculations to elucidate both structure and conformational properties. Thus the spin distribution in these species is typical of (T-radicals with a pyramidal center at sulfur and in accord with the solid-state ESR data. 

Transannular interaction via the electron-delocalization mechanism was found, but lessened by 10-15% for the ligand superhyperfine splitting and 30-35% for the hyperfine splitting (62) in the epr spectrum. The crystal structure of [VOS2CNEt2)2] shows that the molecular core has the expected C2V symmetry [V-0 = 159.1(4), V-S = 138.7(2)-241.0(2) pm] (63). Magnetic and spectral data provided evidence for a tetragonal, pyramidal structure (VII) for these complexes. Like many other coordinatively unsaturated, metal... 

In Table 3 are listed the proton hyperfine splittings (o ) for. the anion and cation radicals of heptafulvalene, calculated using McConnell s... 

It can be noticed there are two types of hydrogen atoms atoms 1-5 lying in the molecular plane and atoms 6 and 7 lying out of the plane. Thus, the hyperfine splitting constants (an) cannot be interpreted by means of one relationship, but the expressions... 

Yonezawa and collaborators (99) have reported unrestricted open-shell SCF calculations where the one-center exchange integrals were taken into account their treatment concerned allyl, vinyl, and nitrogen dioxide radicals. The one-center exchange integrals also are involved in the INDO method (85). Here, the following relationship for hyperfine splitting constants holds ... 

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