The reactions between CrO2Cl2 and a series of silanes have been investigated using matrix isolation infrared spectroscopy. Twin-jet codeposition of the two reagents into argon matrices at 14 K followed by irradiation with light of lambda > 300 nm led to the growth of a number of new bands. These have been assigned to the appropriate silanol species formed by oxygen insertion into the Si-H bond, strongly complexed to CrCl2O. The structures and vibrational frequencies of these complexes have been characterized by high-level theoretical calculations. These calculations also support the relative preference for the insertion reaction compared to other possible pathways. Merged-jet codeposition of SiH2Cl2 with CrO2Cl2 at 200 degrees C also led to the formation of the free silanol, HSiCl2OH.