Substituent effect on the energy barrier for σ-bond formation from π-single-bonded species, singlet 2,2-dialkoxycyclopentane-1,3-diyls

Abstract

Background: Localized singlet diradicals are in general quite short-lived intermediates in processes involving homolytic bond-cleavage and formation reactions. In the past decade, long-lived singlet diradicals have been reported in cyclic systems such as cyclobutane-1,3-diyls and cyclopentane-1,3-diyls. Experimental investigation of the chemistry of singlet diradicals has become possible. The present study explores the substituents and the effect of their substitution pattern at the C(1)–C(3) positions on the lifetime of singlet octahydropentalene-1,3-diyls to understand the role of the substituents on the reactivity of the localized singlet diradicals.Results: A series of singlet 2,2-dialkoxy-1,3-diaryloctahydropentalene-1,3-diyls DR were generated in the photochemical denitrogenation of the corresponding azoalkanes AZ. The ring-closed products CP, i.e., 3,3-dialkoxy-2,4-diphenyltricyclo[3.3.0.02,4]octanes, were quantitatively obtained in the denitrogenation reaction. The first-order decay process (k = 1/τ) was observed for the fate of the singlet diradicals DR (λmax ≈ 580–590 nm). The activation parameters, ΔH‡ and ΔS‡, for the ring-closing reaction (σ-bond formation process) were determined by the temperature-dependent change of the lifetime. The energy barrier was found to be largely dependent upon the substituents Ar and Ar’. The singlet diradical DRf (Ar = 3,5-dimethoxyphenyl, OCH2Ar’ = OCH2(3,5-dimethoxyphenyl)) was the longest-lived, τ293 = 5394 ± 59 ns, among the diradicals studied here. The lifetime of the parent diradical DR (Ar = Ph, OCH2Ar’ = OCH3) was 299 ± 2 ns at 293 K.Conclusion: The lifetimes of the singlet 1,3-diyls are found to be largely dependent on the substituent pattern of Ar and Ar’ at the C(1)–C(3) positions. Both the enthalpy and entropy effect were found to play crucial roles in increasing the lifetime.