The relative energies and structures of 2-pyrimidinethiol (1), 4-methyl-2-pyrimidinethiol (3), 5-methyl-2-pyrimidinethiol (5), and 4,6-dimethylpyrimidinethiol (7), and their dimers, disulfides, sulfenyl radicals, and tautomers have been studied using restricted and unrestricted ab initio theory, density functional theory, complete basis set methods, coupled cluster theory, and quadratic configuration interaction calculations. The electrochemical oxidation of 2-pyrimidinethiol (1), 4-methyl-2-pyrimidinethiol (3), and 4,6-dimethylpyrimidinethiol (7) in ethanenitrile affords the respective disulfides in excellent yields. The less polar 2-pyrimidinethiol tautomers are predicted to be the dominant species in the gas phase. CBS-QB3, CBS-Q, CCD, CCSD(T), QCISD(T), and MP2 predict the energy difference (Ere,) between (1) and its tautomer (2-pyrimidinethione, 2) to be in the narrow range from 7.23 to 7.87 kcal/mol. Similar trends are observed in the Ere, values for the respective tautomers of 2-pyrimidinethiols (3), (5), and (7). The hybrid density functionals B3LYP, B3P86, B3PW91, and MPW1PW91 predict smaller values for Ere, between the tautomers than any of the other models. Substitution of methyl groups at positions 4 and 6 of the pyrimidine ring lowers the energy difference between the respective tautomers while a methyl group at position 5 has little effect. The 2-pyrimidinethiol dimer (13) is predicted to be 5.52 and 4.12 kcal/mol, respectively, lower in energy than the isomeric 2-pyrimidinethione dimer (14) and heterodimer (15). The intramolecular four center transition states (TS1) for the tautomerization of 2-pyrimidinethiols (1, 3a, 3b, 5, and 7) in the gas phase have activation barriers of 34.84, 34.42, 34.02, 35.16, and 33.64 kcal/mol, respectively. Alternative lower energy pathways for tautomerism in the gas phase involve dimers and dimer transition states. Dimers and dimer transition states are also involved in the electrochemical oxidation of the 2-pyrimidinethiols. The APT, Mulliken (MPA), and NBO partial atomic charges are compared with the CHELPG and MKS charges that give the most consistent and similar results.