Transesterified organosilicon compounds, including ionic organosilicon compounds and coupling agents, and aqueous-based compositions including transesterified organosilicon compounds are provided. Compositions comprising at least one transesterified organosilicon are suitable for application to various inorganic, organic and cullulosic surfaces for imparting water repellency and improved wetting. Compositions comprising transesterified organosilicon compounds exhibit reduced flammability, improved hydrolytic stability, reduced gloss and improved water repellency while maintaining reactivity with various substrates.