Treatment of Zn(Si(SiMe3)(3))(2) with ZnX2 (X = Cl, Br, I) in tetrahydrofuran (THF) at 23 degrees C afforded [Zn(Si(SiMe3)(3))X(THF)](2) in 83-99% yield. X-ray crystal structures revealed dimeric structures with Zn2X2 cores. Thermogravimetric analyses of [Zn(Si(SiMe3)(3))X(THF)](2) demonstrated a loss of coordinated THF between 50 and 155 degrees C and then single-step weight losses between 200 and 275 degrees C. The nonvolatile residue was zinc metal in all cases. Bulk thermolyses of [Zn(Si(SiMe3)(3))X(THF)](2) between 210 and 250 degrees C afforded zinc metal in 97-99% yield, Si(SiMe3)(3)X in 91-94% yield, and THF in 81-98% yield. Density functional theory calculations confirmed that zinc formation becomes energetically favorable upon THF loss. Similar reactions are likely to be general for M(SiR3)(n)/MXn pairs and may lead to new metal-film-growth processes for chemical vapor deposition and atomic layer deposition.