Publication Details (including relevant citation information):
J. Am. Chem. Soc. 2011 133, 180-183
Reaction of a digermyne with cyclooctatetraene (cot) gave two isomeric products. A Ge(II) inverse sandwich is formed as the kinetic product, which was a result of complete Ge≡Ge bond cleavage and the formation of a π-bound cot ring. This isomerized in solution at room temperature over a period of 5 days to give the thermodynamic product, a tetracyclic diene-digermane, in which a single-bonded Ge—Ge moiety has inserted into a C═C bond of the cot carbocycle. Kinetic studies afforded an activation enthalpy (ΔH‡) and entropy (ΔS‡) of 14.9 kcal mol−1 and −6.2 cal mol−1 K−1 respectively. Heating crystals of the thermodynamic product at ca. 120 °C cleanly regenerated the original inverse sandwich isomer.
Address (URL): http://dx.doi.org/10.1021%2Fja107380p