Laser-ablated Sc atoms react with CO2 molecules to give primarily the insertion product, OScCO, and a minor amount of the addition product, Sc-(eta(2)-OC)O, which have been isolated in a solid argon matrix. Photoisomerization to form the novel side-bonded OSc-(eta(2)-CO) isomer and photoionization to the OScCO+ cation and OScOC+ and ScOCO+ isomers proceed upon different wavelength photolyses. The product absorptions were identified by isotopic substitution and density functional calculations of isotopic frequencies. Similar experiments with Y give spectra for the analogous product molecules and cations.