In this work the nucleophilic addition of water and methanol to the dicyanonitrosomethanide anion (dcnm, [C(CN)(2)(NO)](-)) in the absence of the usual transition metal promoters was investigated. Experimentally it was shown that a quantitative conversion of the dcnm anion to carbamoylcyanonitrosomethanide (ccnm, [C(CN)(CONH2)(NO)](-)) by the addition of 1 equiv of water to a nitrile group is complete in 48 h at 100 degrees C, or in 1.5 h at 150 degrees C when the reaction is conducted in a microwave reactor. Attempts to add a second equivalent of water to the anion failed with thermal degradation of the anion occurring at 200 degrees C. Ab initio calculations show that the reaction proceeds via three distinct transition states: (1) the transfer of a proton from a water molecule to the nitrile group, (2) the subsequent attack of the generated hydroxide anion on the carbon atom of the nitrile group, and (3) a rapid proton transfer to form a carbamoyl group. The attacking water molecule is shown to be a stronger proton donor when modeled as part of a hydrogen-bonded three water molecule chain, leading to a significant reduction in the reaction barrier. Only the anti-ccnm anion is formed in the reaction. There is a high-energy barrier to the formation of the syn isomer by the rotation of the nitroso group. While the syn isomer of ccnm is shown to be the more thermodynamically stable conformation, examination of the HOMO-1 molecular orbital that arises during the second transition state of the reaction indicates the addition of the hydroxide anion to the carbon atom is forbidden due to orbital symmetry, with a similar effect responsible for the failure of a second equivalent of water to add to the ccnm anion. Under analogous reaction conditions the addition of 1 equiv of methanol to dcnm to form cyano(imino(methoxy)methyl)nitrosomethanide (cmnm, [C(CN)(C(OMe)NH)(NO)](-)) failed, although ab initio calculations initially indicated the reaction should proceed more readily than the addition of water. When the energy required to break the hydrogen-bonded cyclic hexamers in methanol is taken into consideration, the energy barrier to the first transition step is greatly increased. The addition of a second equivalent of methanol to cmnm is unlikely to occur even in the presence of a transition metal as the resultant anion would be marginally thermodynamically unstable.