The initial steps of the reaction of TiCl4 with CH3OH and its isotopomers have been investigated using matrix isolation with infrared spectroscopic detection of the reaction intermediates. When twin jet deposition was employed, a substantial yield of a 1:1 adduct was observed. However, when merged jet deposition was employed with a 15 cm merged reaction region, no traces of the precursors or the 1:1 complex were observed. Rather, very intense bands due to previously unreported monomeric Cl3TiOCH3 were observed, as well as bands due to HCl. Band assignments were assisted by extensive isotopic labeling and supported by density functional calculations. In subsequent experiments, heating the merged region to as high as 350 degrees C led to complete destruction of the bands to Cl3TiOCH3 while bands due to CH3Cl and the complex of CH3Cl with HCl were observed to grow.