Abstract: The reaction of atomic titanium with nitrous oxide has been reinvestigated using matrix isolation in solid neon coupled to infrared spectroscopy and by quantum chemical methods. Our technique of sublimation of Ti atoms from a filament heated at about 1500 °C allowed the formation of three species: one Ti–N2O pair of van der Waals (vdW) type characterized by small red shift with respect to N2O monomer, and two isomers of OTi–N2 pair where N2 is in interaction with the OTi moiety either with end-on or side-on structure...