Abstract
In the course of a series of thermochemical studies on gaseous cyclopentadienyl-metal complexes we have investigated the intramolecular 1,5-transfer of hydrogen and the Si(CH 3) 3 group and the composition of equilibrated mixtures of the x-(trimethylsilyl)cyclopentadiene (= x-TSCP) isomers. For the equilibria 5 − TSCP ⇄ 2 1 1 − TSCP ⇄ 4 3 2 − TSCP the following Van 't Hoff relationships have been derived: log K 1.2=(0.193±0.014)−(1.56±0.03)/θ and log K 3.4=(0.09±0.03)−(0.84±0.05)/θ where θ equals 4.58·10 −3 T (°K). In contrast to the carbon analogues, the 5-isomer is thermodynamically the most stable isomer. The data are used to derive intrinsic differences in incremental data for entropy and enthalpy contributions in specific carbon-silicon compounds. Vapour pressure measurements on equilibrated isomer mixtures yielded log p(mm)=(7.79±0.10) − (2029±31)/ T(°K) resulting in a heat of vaporization Δ H v of 9.28±0.14 kcal/mode.
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