1731-10-8Relevant articles and documents
Metathesis of silicon-containing olefins
Finkel'shtein,Ushakov,Portnykh
, p. 133 - 144 (1992)
The behaviour of various olefins containing Si-C, Ge-C, Si-Si, Si-H, Si-O-Si and Si-O-C bonds has been studied in the presence of rhenium on alumina metathesis catalysts. Monovinyl-, allyl-, and butenylsilanes bearing alkyl, alkenyl, aryl, aralkyl, silacycloalkyl, siloxane and hydride substituents, as well as unsaturated silacarbon heterocycles, mono- and diallylgermanes, were used as substrates. Heterogeneous Re2O7/Al2O3-SnBu4 and Re2O7/Al2O3-PbEt4 catalysts showing good activity in metathesis were examined. Except for hydrides, allyl- and butenylsilanes or germanes were active in metathesis regardless of the nature of the substituents at the metal atom. On the other hand, all of the vinylsilanes used were practically inactive in the reaction. Except for vinyl derivatives, metathesis of di- and polyalkenylsilanes, disilanes, disiloxanes and germanes occurred via both intermolecular and intramolecular pathways. These were used to develop a novel effective synthetic method for producing linear 1,4-bis(triorganylsilyl)-(or germyl-) but-2-enes (including those with ferrocenyl substituents at the silicon) and six-membered mono- and disilacycloalkenes, as well as silaspirane structures. It was shown that α-olefin co-metathesis with allylsilanes (followed by protodesilylation) is a convenient method for increasing the length of an α-olefin hydrocarbon chain.
Kinetics and mechanism of the thermal decomposition of 1,1-dimethylgermetane
Namavari, Mohammed,Conlin, Robert T.
, p. 3307 - 3312 (2008/10/08)
The gas-phase unimolecular decomposition of 1,1-dimethylgermetane has been investigated over the temperature range 683.9-751.2 K at pressures of ca. 15 Torr. Four products, cyclopropane, propene, ethene, and 1,1,2,2-tetramethylgermacyclopentane, are formed. Arrhenius parameters for the primary decomposition channels to (1) 1,1-dimethylgermene and ethene and (2) dimethylgermylene, cyclopropane, and propene are reported: (1) log k1/s-1 = 14.7 ± 0.4 - 63.1 ± 1.2 kcal mol-1/RT ln 10; (2) log k2/s-1 = 14.1 ± 0.3 - 60.7 ± 0.8 kcal mol-1/RT ln 10. (Matrix Presented) The surprisingly high activation energy for the 2 + 2 cycloreversion is interpreted in terms of a strong Ge-C bond dissociation enthalpy and/or reduced ring strain in the germetane.