Kinetic Studies on the Thermal Decomposition oftrans-2,3-Dimethyl-1-tri-tert-butylsilyl-1-triisopropylsilylsilirane and the Mechanism of Silylene Generation
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Abstract
trans-2,3-Dimethyl-1-tri-tert-butylsilyl-1-triisopropylsilylsilirane (1) has been prepared in 98% yield by the treatment of (tBu3Si)(iPr3Si)SiBr2 with activated magnesium in the presence of trans-2-butene. Trapping studies suggested that silylene (tBu3Si)(iPr3Si)Si: (2) was extruded by thermolysis of 1. Without added trapping agents self-trapping of silylene 2 formed a stable product, 1,1-di-tert-butyl-4,4-dimethyl-2-triisopropylsilyl-1,2-disiletane (5), by intramolecular C−H insertion. Thermolysis of 1 presented an ideal reaction for a kinetic study of the thermal decomposition of a silirane. It was found that thermal decomposition of 1 is stereospecific and first-order in benzene solution. From the rates of reaction at various temperatures activation parameters were obtained. The results were consistent with a non-least motion pathway for silylene retroaddition and hence addition.
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