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Theoretical Study On the Effect of α-Substituents On the Properties of Vinyl Radicals

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The effect of α-substituents on the structures, inversion barriers (Einv) and isotropic 13Cα hyperfine splitting constants (a(13Cα) of vinyl radicals CH2=C(.)-Y has been determined by ab initio calculations. The degree of bending at the central carbon decreases slightly with decreasing electronegativity of σ-type αsubstituents, the optimum CCY bond angle  being in the range 130÷150° at the UMP2/TZP level. On the other hand, Einv and a(13Cα) decrease strongly as the electronegativity of α-substituents decreases. The linear structure is favoured in the trisilylvinyl radical in accord with ESR evidences. This configuration is not found to be the more stable when Y contains a π-system capable of delocalizing the unpaired electron such as in the -CN=N and -C(=O)OH groups as previously suggested. However, the inversion barrier is computed to be small (Einv = 1.4 and 2.8 kcal mol-1, respectively, at the UQCISD/TZP//UMP2/TZP level). This finding is in accord with recent studies of stereoselectivity.

Affiliations: 1: I. Co. C.E.A.-C.N.R., Area della Ricerca, Via Gobetti 101, 40129 Bologna, Italy


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