We have conducted an extensive computational study of the structural and energetic properties of select acetonitrile-Group IV (A & B) tetrahalide complexes, both CH3CN-MX4 and (CH3CN)2-MX4 (M = Si, Ge, Ti; X = F, Cl). We have also examined the reactivity of CH3CN with SiF4, SiCl4, GeCl4, and TiCl4, and measured low-temperature IR spectra of thin films containing CH3CN with SiF4, GeCl4, or TiCl4. The six 1:1 complexes fall into two general structural classes. CH3CN-TiCl4, CH3CN-TiF4, and CH3CN-GeF4, exhibit relatively short M-N bonds (~2.3 Å), an intermediate degree of distortion in the MX4 subunit, and binding energies ranging from 11.0 to 13.0 kcal/mol. Conversely, CH3CN-GeCl4, CH3CN-SiF4, and CH3CN-SiCl4, are weakly bonded systems, with long M-N distances (>3.0 Å), little distortion in the MX4 subunit, and binding energies ranging from 3.0 to 4.4 kcal/mol. The structural features of analogous 2:1 systems resemble those of their 1:1 counterparts, whereas the binding energies (relative to three isolated fragments) are roughly twice as large. Calculated M-N potential curves in the gas phase and bulk, dielectric media are reported for all 1:1 complexes, and for two systems, CH3CN-GeF4 and CH3CN-SiF4, these data predict significant condensed-phase structural changes. The effect on the CH3CN-SiF4 potential is extreme; the curve becomes quite flat over a broad range in dielectric media, and at higher ε values, the global minimum shifts inward by about 1.0 Å. In bulk reactivity experiments, no reaction was observed between CH3CN and SiF4, SiCl4, or GeCl4, whereas CH3CN and TiCl4 were found to react immediately upon contact. Also, thin-film IR spectra indicate a strong interaction between CH3CN and TiCl4, yet only weak interactions between CH3CN and GeCl4 or SiF4 in the solid state.