Study of the reactione + e −→K + K − in the energy range1350 \leqq \sqrt s \leqq 2400 MeV

Thee ⁺ e ^?→K ⁺ K ^? cross section has been measured from about 750 events in the energy interval \(1350 \leqq \sqrt s \leqq 2400 MeV\) with the DM2 detector at DCI. TheK ^± form factor |F _F ^±| cannot be explained by the ρ, ω, ? and ρ′(1600). An additional resonant amplitude at 1650 MeV has to be added as suggested by a previous experiment.     

Group additive values for the gas phase standard enthalpy of formation of hydrocarbons and hydrocarbon radicals

A complete and consistent set of 95 Benson group additive values (GAV) for the standard enthalpy of formation of hydrocarbons and hydrocarbon radicals at 298 K and 1 bar is derived from an extensive and accurate database of 233 ab initio standard enthalpies of formation, calculated at the CBS-QB3 level of theory. The accuracy of the database was further improved by adding newly determined bond additive corrections (BAC) to the CBS-QB3 enthalpies. The mean absolute deviation (MAD) for a training set of 51 hydrocarbons is better than 2 kJ mol(-1). GAVs for 16 hydrocarbon groups, i.e., C(C(d))(3)(C), C-(C(d))(4), C-(C(t))(C(d))(C)(2), C-(C(t))(C(d))(2)(C), C-(C(t))(C(d))(3), C-(C(t))(2)(C)(2), C-(C(t))(2)(C(d))(C), C-(C(t))(2)(C(d))(2), C-(C(t))(3)(C), C-(C(t))(3)(C(d)), C-(C(t))(4), C-(C(b))(C(d))(C)(H), C-(C(b))(C(t))(H)(2), C-(C(b))(C(t))(C)(H), C-(C(b))(C(t))(C)(2), C(d)-(C(b))(C(t)), for 25 hydrocarbon radical groups, and several ring strain corrections (RSC) are determined for the first time. The new parameters significantly extend the applicability of Benson's group additivity method. The extensive database allowed an evaluation of previously proposed methods to account for non-next-nearest neighbor interactions (NNI). Here, a novel consistent scheme is proposed to account for NNIs in radicals. In addition, hydrogen bond increments (HBI) are determined for the calculation of radical standard enthalpies of formation. In particular for resonance stabilized radicals, the HBI method provides an improvement over Benson's group additivity method.     

The crystal structure of bis(triphenylphosphine)-(η-cyclohexa-1,3-diene)rhenium trihydride

Bis(triphenylphosphine)(η-cyclohexa-1,3-diene)rhenium trihydride, (Ph₃P)₂(η-C₆H₈)ReH₃ (I) crystallises in the space group C2/c with cell dimensions a 22.76(2), b 10.14(1) c 29.813(6) Å, β 97.69(8)°. The final refinement of 126 variables using 1580 non-zero reflections resulted in a final R value of 0.064. In spite of uncertainties in some of the atomic positions, the structure of I is compatible with a trihydrido diene compound with a distorted pentagonal bipyramidal configuration, rather than with a dihydrido cyclohexenyl compound having an “agostic” CH ? Re interaction. The factors which govern the structure of the complexes (Ph₃P)₂(η-1,3-diene)ReH₃ are discussed.     

Poly(vinyl chloride) stabilization with organo-tin compounds: Part VI—The behavior of dibutyltin dilaurate

The reaction between dibutyltin dilaurate (DBTL) and chloro-4-hexene-2 (containing its isomer chloro-2-hexene-3) as a model compound for the allylic chlorine atom in poly(vinyl chloride) has been studied in dichlorobutane solution at 80°C. The reactions observed—elimination of HCl to give hexadiene and substitution of the laurate group to give hexenyl laurate—are believed to obey E2 and SN2 mechanisms through a common intermediate carbocation, with a rather low selectivity towards the substitution owing to the associated structure of the DBTL. The kinetics are complex because of the complex nature of the exchange reaction between DBTL and Bu₂SnCl₂. A reverse reaction between the hexenyl laurate and the organo-tin chloride is proposed to explain the limitation of the substitution reaction.     

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