Gas-phase kinetics of chlorosilylene reactions II. ClSiH + C2H4: absolute rate measurements and quantum chemical and RRKM calculations for the prototype pi addition reaction

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1-silacyclopent-3-ene, are carried out to obtain rate constants for its bimolecular reaction with ethene, C2H4, in the gas-phase. The reaction is studied over the pressure range 0.13-13.3 kPa (with added SF6) at five temperatures in the range 296-562 K. The second order rate constants, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1))=(-10.55 +/- 0.10) + (3.86 +/- 0.70) kJ mol(-1)/RT ln10. The Arrhenius parameters correspond to a loose transition state and the rate constant at room temperature is 43% of that for SiH2 + C2H4, showing that the deactivating effect of Cl-for-H substitution in the silylene is not large. Quantum chemical calculations of the potential energy surface for this reaction at the G3MP2//B3LYP level show that, as well as 1-chlorosilirane, ethylchlorosilylene is a viable product. The calculations reveal how the added effect of the Cl atom on the divalent state stabilisation of ClSiH influences the course of this reaction. RRKM calculations of the reaction pressure dependence suggest that ethylchlorosilylene should be the main product. The results are compared and contrasted with those of SiH2 and SiCl2 with C2H4.

Tarabotti fra storia e storiografia: miti, fatti e alcune questioni più generali

This article presents the state of the arts about suor Arcangela Tarabotti, once "little less than a foot-note" well-known to scholars only (even if by Benedetto Croce, the most important of all XXth century Italian historians) and nowadays a literary case and a well-recognised proto-feminist, whose works are now all translated into English. The article examins the fortune (or misfortune) she enjoyed over the centuries, the reasons of her current international success, her life according to real documents and to her more fantasist accounts, the archives research and recent publications on her. It also explores the theoretical issues currently in place within Italian women's studies, moving from the 1970s' emphasis on witches, to the 1980s' passion for women saints, and the current obsession with queens and "winners", in order to prove that Arcangela Tarabotti was someonw unique who paid an enormous price for her bravery and outspokness, having been cloistered without a religious vocation.