The development of reactive organometallics has become a vital part synthetic chemistry. Organosilanes potentially represent a cheap, robust, and environmentally benign precursor to reactive organometallics, but the nature of the very stable C−Si bond has generally prevented their use as precursors to more reactive organometallics. We present investigations into copper fluoride complexes which activate organosilanes in anhydrous media under mild conditions, effecting transmetalation to produce stable and in some cases isolable organocopper species containing sensitive functional groups including carbonyl groups, aryl bromides, benzylic chlorides, and alkyl ketones. This discovery allows us to better understand the fundamental reactivity of presumed intermediates in copper-catalyzed reactions and to develop new catalytic bond-forming processes including allylations of aldehydes, 1,4-addition of vinyl epoxides, and intramolecular ring closures.