Geometry of radicals

A great deal of information on the electronic structure and geometry of radicals in solution can be extracted from their ESR spectra, as it is well established that the values of hyperfine coupling constants (hfcc), arising from the spin density of the s-orbitals, markedly increase with increasing of the SOMO s-character. The pyramidalization of the radicals is manifested in higher values of their hfccs (o-radicals), whereas smaller values of the hfccs are indicative of the more planar radicals (tt-radicals). 

Fluorination has dramatic effects on the geometry of radicals. In-Repulsive interactions of a-fluorination cause radicals to revert to pyramidal forms (pyramidalize).87-95... 

Several possible relationships between the geometries of radical cations and their precursors are shown schematically in Fig. 15. In addition to the purely... 

The rate-determining step in the Na/NH3 reduction of alkynes is the protonation of the radical anion A. The next step, the reaction of the alkenyl radical C to the alkenyl-sodium intermediate B, determines the stereochemistry. The formation of B occurs such that the substituents of the C=C double bond are in trims positions. This trans-selectivity can be explained by product-development control in the formation of B or perhaps also by the preferred geometry of radical C provided it is nonlinear at the radical carbon. The alkenylsodium compound B is protonated with retention of configuration, since alkenylsodium compounds are configurationally stable (cf. Section 1.1.1). The Na/NH3 reduction of alkynes therefore represents a synthesis of fnms-alkencs. 

Ab initio calculations of geometry of radical with SiHj instead of Si(CH3)3 group. 

EPR studies and other physical methods have provided the basis for some insight into the detailed geometry of radical species. Deductions about structure can also be drawn from the study of the stereochemistry of reactions involving radical intermediates. Several structural possibilities must be considered. If discussion is limited to alkyl radicals, the possibilities would include a rigid pyramid, rapidly inverting pyramids, or a planar trigonal structure ... 

The notions of eclipsing and gauche interactions are applicable not only to stable organic structures, but also to reactive intermediates. In fact, as described in the next Going Deeper highlight, the geometry of radicals is influenced by a conformational effect similar to those discussed for standard alkanes. 

There have been many studies aimed at deducing the geometry of radical sites by examining the stereochemistry of radical reactions. The most direct kind of study involves the generation of a radical at a carbon which is a stereogenic center. A planar or rapidly invertirjg radical would lead to racemization, whereas a rigid pyramidal structure should... 

The EPR spectra of a number of bridgehead radicals have been measured and the hyperfine couplings measured (see Section 12.2.3). Both the and couplings are sensitive to the pyramidal geometry of the radical." " The reactivity of bridgehead radicals increases with increased pyramidal character." ... 

G. Herzberg (Ottawa) contributions to the knowledge of electronic structure and geometry of molecules, particularly free radicals. 

Examine the geometry of the most stable radical. Is the bonding in the aromatic ring fuUy delocalized (compare to model alpha-tocopherol), or is it localized Also, examine the spin density surface of the most stable radical. Is the unpaired electron localized on the carbon (oxygen) where bond cleavage occurred, or is it delocalized Draw all of the resonance contributors necessary for a full description of the radical s geometry and electronic structure. 

First examine the geometry of methyl radical. Is it planar or puckered Examine the geometries of 2-methy 1-2-propyl radical, trifluoromethyl radical, trichloromethyl radical and tricyanomethyl radical. Classify each of the substituents (methyl, fluoro, chloro and cyano) as a n-electron donor or as a Tt-electron acceptor (relative to hydrogen). Does replacement of the hydrogens by 7t-donor groups make the radical center more or less puckered Does replacement by Jt-acceptor groups make the radical center more or less puckered Justify your observations. 

Examine the structures of the two transition states (chlorine atom+methane and chlorine+methyI radical). For each, characterize the transition state as early (close to the geometry of the reactants) or as late (close to the geometry of the products) In Ught of the thermodynamics of the individual steps, are your results anticipated by the Hammond Postulate Explain. 

Repeat your analysis for n-propylbenzene. (Compare geometries of 1-propylbenzene radical cation and 1-propylbenzene.) Where would you expect a strong peak in the mass spectrum Identify the ion responsible. 

The rate of radical addition is most dramatically affected by substituents either at the site of attack or at the radical center. Remote substituents generally have only a small influence on the stereochemistry and regiospecificity of addition unless these groups are very bulky or the geometry of the molecules is constrained (e.g. intramolecular addition - Section 1,2.4). 

A number of radical anions of sulfur-containing aromatic compounds have been studied essentially by means of ESR spectroscopy and sometimes by electronic spectroscopy. The studied compounds include aromatic rings separated by the oxidized sulfur functionality. The effects caused by the latter depend on the geometry and topology of the aromatic systems as well as on the electron-withdrawing ability of the other substituents. 

Four IR absorption bands have been identified in the spectrum of the hydroxysulfonyl radical (HOSO 2) which has been obtained by the reaction of hydroxyl radicals with sulfur dioxide in argon matrix at 11 K16. The observed bands at 3539.9 and 759.5 cm 1 have been assigned to O—H and S—OH stretching modes while the bands at 1309.2 and 1097.3 cm-1 have been assigned to the asymmetric and symmetric stretching modes of the double bonded S02 moiety. These data are consistent with the theoretical prediction on the geometry of the hydroxysulfonyl radical12. 

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