Substituent effects on benzyl radical hyperfine coupling constants. Part 2. The effect of sulphur substituents

1984 ◽  
Vol 62 (6) ◽  
pp. 1164-1168 ◽  
Author(s):  
Danial D. M. Wayner ◽  
Donald R. Arnold
Keyword(s):  
Electron Spin Resonance ◽  
Spin Density ◽  
Oxidation State ◽  
Esr Spectroscopy ◽  
Hyperfine Coupling ◽  
Substituent Effects ◽  
Coupling Constants ◽  
Benzyl Radical ◽  
Spin Resonance ◽  
Benzyl Radicals

Several 4-substituted benzyl radicals of the general form R(On)SC6H4CH2•(n = 0, 1, 2; R = Me, Ph, Tol, COCH3 OCH3) have been investigated by electron spin resonance (esr) spectroscopy. In general, the ability to delocalize spin density onto the substituent decreases as n increases. The effect of R on the spin density depends on the oxidation state of the sulphur. These trends are explained by considering the sulphur to be either a spin donor or a spin acceptor, depending on the oxidation state. The σ•α values are determined.

A comparison of electron spin resonance α- and β-hyperfine coupling constants in para-substituted α-phenethyl radicals

1986 ◽  
Vol 64 (4) ◽  
pp. 769-772 ◽  
Author(s):  
Donald R. Arnold ◽  
A. Martin de P. Nicholas ◽  
Kent M. Young
Keyword(s):  
Electron Spin Resonance ◽  
Experimental Evidence ◽  
Linear Relationship ◽  
Electron Spin ◽  
Hyperfine Coupling ◽  
Coupling Constants ◽  
Hyperfine Coupling Constants ◽  
Spin Resonance ◽  
Benzyl Radicals ◽  
Spin Delocalization

The linear relationship between the electron spin resonance hyperfine coupling constants (hfc) of the α- and β-hydrogens of para-substituted α-phenethyl radicals provides experimental evidence that the magnitude of both the α- and β -hfc is determined largely by the extent of spin delocalization in these benzylic systems. The [Formula: see text] scale, developed using substituted benzyl radicals, is shown to apply to phenethyl radicals as well.

Substituent effects on benzylic radical hydrogen hyperfine coupling constants. Part 4. The effect of branching of the alkyl substituent

1985 ◽  
Vol 63 (9) ◽  
pp. 2378-2383 ◽  
Author(s):  
Danial D. M. Wayner ◽  
Donald R. Arnold
Keyword(s):  
Hyperfine Coupling ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Esr Spectra ◽  
Coupling Constants ◽  
Molecular Orbital Calculations ◽  
Methyl Ethyl ◽  
Hyperfine Coupling Constants ◽  
Benzyl Radical ◽  
Spin Resonance

The effects of substituents in the meta and para positions of the benzyl radical on the α-hydrogen hyperfine coupling constants (hfc's) are discussed. The electron spin resonance (esr) spectra of the para-methyl, ethyl, isopropyl, and tert-butyl substituted benzyl and cumyl radicals are analysed. Hyperconjugation involving the C—C bond is 40–60% as effective as C—H hyperconjugation for delocalizing spin density. This conclusion is supported by INDO molecular orbital calculations. Similar analysis of the 13Cmr spectra of the para-alkyl substituted cumyl carbocations provides evidence that C—C hyperconjugation is 75–90% as effective as C—H hyperconjugation for delocalizing charge density.

Substituent effects on benzyl radical hydrogen hyperfine coupling constants (hfc's).: Part 5. The comparison of electron spin resonance hfc's and the stabilization energy of π-radicals due to spin delocalization

1986 ◽  
Vol 64 (2) ◽  
pp. 270-276 ◽  
Author(s):  
A. Martin de P. Nicholas ◽  
Donald R. Arnold
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Substituent Effects ◽  
Energy Scale ◽  
Spin Systems ◽  
Stabilization Energy ◽  
Coupling Constants ◽  
Spin Resonance ◽  
Benzyl Radicals ◽  
Spin Delocalization

Electron spin resonance (esr) hfc values of π-radicals are found to be linearly related to the stabilization energy due to spin delocalization. Application of this relationship to benzyl radicals permits the representation of σ•α values on an energy scale. Mulliken charges in the α- and β-spin systems are found to provide valuable information about factors governing the effects of substituents on spin delocalization in benzyl radicals. These effects can be rationalized by considering four types of spin–spin interactions involving σ- and π-electrons in the α- and β-spin systems. The Mulliken analysis shows that all substituents are stronger π α-acceptors (or weaker π α-donors) at the para position relative to the meta position. Similarly, in the 3 system the meta derivatives are the better acceptors. This may be understood in terms of the excess of π α-spin at the para-carbon and the excess of π β-spin at the meta-carbon. Similar effects are observed in the a framework.

Substituent effects on benzyl radical hyperfine coupling (hfc) constants. Part 3. Comparison of the α-hfc for substituted benzyl radicals with the β-hfc for substituted cumyl radicals

1985 ◽  
Vol 63 (5) ◽  
pp. 1150-1155 ◽  
Author(s):  
Donald R. Arnold ◽  
A. Martin De P. Nicholas ◽  
Miles S. Snow
Keyword(s):  
Hyperfine Coupling ◽  
Linear Regression Analysis ◽  
Substituent Effects ◽  
Esr Spectra ◽  
Charge Effects ◽  
Benzyl Radical ◽  
Spin Resonance ◽  
Benzyl Radicals ◽  
Spin Delocalization ◽  
The Relationship

The electron spin resonance (esr) spectra of eighteen para-substituted cumyl radicals were analyzed. The relationship between the β-hyperfine coupling (β-hfc) constants of these cumyl radicals and the corresponding α-hfc constants of benzyl radicals was studied. Although there is a general trend for the α- and β-hfc values to vary in a similar manner, specific deviations from a linear correlation between these parameters were observed. These deviations were rationalized by considering charge effects on spin delcoalization. The correlation coefficient for the linear regression analysis of these α- and β-hfc values was found to significantly improve when β arameters reflecting charge effects on spin delocalization were included in an extended Hammett treatment of the spectral data.

Notizen: 13C-NMR an paramagnetischen Phenylmetallocenen1: Analogie zum Benzylradikal.

1976 ◽  
Vol 31 (8) ◽  
pp. 1153-1154 ◽  
Author(s):  
Frank H. Köhler ◽  
G. Matsubayashi
Keyword(s):  
Density Distribution ◽  
Spin Density ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Hyperfine Coupling ◽  
Spin Density Distribution ◽  
Coupling Constants ◽  
Methyl Radicals ◽  
Benzyl Radical ◽  
C Nmr

The 13C NMR spectra of seven phenylated paramagnetic metallocenes have been recorded. From the spectra the 13C hyperfine coupling constants A(13C) have been extracted and compared with corresponding A(1H). It is found that the phenyl A′s in nickelocenes and cobaltocenes behave as in benzyl radical being reduced by a factor of 27. This offers a new route to informations about spin density distribution in substituted methyl radicals.

scholarly journals The Coordination Chemistry of Phosphoryl Compounds Containing the -N(CH3)2 Group, XII.

1973 ◽  
Vol 28 (3-4) ◽  
pp. 104-106 ◽  
Author(s):  
M.W.G. De Bolster ◽  
B. Nieuwenhuijse ◽  
J. Reedijk
Keyword(s):  
Electron Spin Resonance ◽  
Metal Ion ◽  
Room Temperature ◽  
Esr Spectroscopy ◽  
Hyperfine Coupling ◽  
Hyperfine Coupling Constant ◽  
Zero Field ◽  
Coupling Constant ◽  
Spin Resonance ◽  
Temperature Electron

Room temperature electron spin resonance powder spectra have been recorded for some compounds of the type Mn(ligand)p(anion)2 with hexamethylphosphoramide and nonamethylimidodiphosphoramide as ligands (p = 1 - 4) and BF-4, NO-3, Cl-, Br-, I- and NCS-as anions.The values for the zero-field parameters, D and λ, have been determined and are compared with literature data. It is shown that ESR spectroscopy can be very helpful in elucidating the structures of manganese(II) complexes.The high values for the hyperfine coupling constant of the solvates suggest that in these complexes the bonding between the ligands and the metal ion is essentially ionic.

Nitroxide derivatives of acetylacetone as spin-labelled ligands

1981 ◽  
Vol 59 (1) ◽  
pp. 156-163 ◽  
Author(s):  
D. Plancherel ◽  
D. R. Eaton
Keyword(s):  
Electron Spin Resonance ◽  
Metal Complex ◽  
Electron Spin ◽  
Hyperfine Coupling ◽  
Esr Spectra ◽  
Enol Form ◽  
Coupling Constants ◽  
Spin Resonance ◽  
Steric Factors ◽  
Derivatives Of

Electron spin resonance spectra are reported from a number of radicals derived from 2,4-pentadione substituted at the 3 position with nitroxide-containing groups. If the substituent is t-butyl nitroxide no metal complexes are formed. This is attributed to steric factors which prevent the formation of the enol form of the β-diketone. If the substituent is trifluoromethyl nitroxide two types of metal complex have been observed. The esr spectra of the first type are very similar to that of the uncomplexed radical. Such complexes are formed with Co(III) and Al(III). The esr spectra of the second type show considerably increased 14N and 19F hyperfine coupling constants and in some cases large couplings to the metal nucleus. Complexes for the second type have been observed with Pd(II), Pt(II), and Rh(III). The possible structures of these radicals are discussed.

Sign in / Sign up

Export Citation Format

Share Document