Reactions of laser-ablated Y and La atoms with H2O2 gives the M(OH)(2) and M(OH)(3) molecules and the HOMO dehydration product, and the cation M(OH)(2)(+) in solid argon. Density functional calculations show that the dihydroxide molecules and cations are bent at the metal center, and the symmetric and antisymmetric O-H stretching modes are both observed in the infrared spectra. The trihydroxide molecules have calculated C-3h structures characterized by strong antisymmetric O-H and M-O stretching modes. Mulliken charges increase for all product molecules going down the Group 3 family and increase as one, two, and three OH ligands are bonded to the metal center. Evidence is also presented for the Y(OH)(4)(-) anion.