Reactions of laser- ablated Mn, Fe, Co, and Ni atoms with H2O2 and with H-2 + O-2 mixtures in excess argon give new absorptions in the O-H and M-O stretching regions, which are assigned to metal dihydroxide and trihydroxide molecules, M(OH)(2) and M(OH)(3). Isotopic substitutions (D2O2, O-18(2), O-16,18(2), D-2) confirmed the assignments and DFT calculations reproduced the experimental results. The O-H stretching frequencies decreased in the dihydroxides from Sc to Zn. Mulliken and natural charge distributions indicate significant electron transfer from metal d orbitals to OH ligands that decreases from Sc to Zn, suggesting that the early transition metal hydroxides are more ionic and that the later transition metal hydroxides are more covalent.