We recently reported a new method for the direct dehydrogenative C-H silylation of heteroaromatics utilizing Earth abundant potassium tert-butoxide. Herein we report a systematic experimental and computational mechanistic investigation of this transformation. Our experimental results are consistent with a radical chain mechanism. A trialkylsilyl radical may be initially generated by homolytic cleavage of a weakened Si-H bond of a hypercoordinated silicon species as detected by IR, or by traces of oxygen which can generate a reactive peroxide by reaction with [KOt-Bu](4) as indicated by density functional theory (DFT) calculations. Radical clock and kinetic isotope experiments support a mechanism in which the C Si bond is formed through silyl radical addition to the heterocycle followed by subsequent beta-hydrogen scission. DFT calculations reveal a reasonable energy profile for a radical mechanism and support the experimentally observed regioselectivity. The silylation reaction is shown to be reversible, with an equilibrium favoring products due to the generation of H-2 gas. In situ NMR experiments with deuterated substrates show that H-2 is formed by a cross-dehydrogenative mechanism The stereochemical course at the silicon center was investigated utilizing a H-2-labeled silolane probe; complete scrambling at the silicon center was observed, consistent with a number of possible radical intermediates or hypercoordinate silicates.