We present a computational study on the concerted hydrolysis of several classes of N-sulfinylamines of generic formula R-N=S=O, such as the -amines themselves (R-NSO), -hydrazines (R-NH-NSO), -hydrazides (R-CO-NH-NSO) and -amides (R-CO-NSO), as these species are known to possess a wide range of hydrolytic reactivity. Two possible mechanisms of hydrolysis, with a water dimer across the S=O and N=S bonds, in the gas phase are investigated. The reactivity is discussed with respect to the electronic structures, established with the use of the quantum theory of Atoms in Molecules, Natural Bond Orbital and Natural Resonance Theory approaches. For the inert N-sulfinyl-hydrazines and the keto tautomers of N-sulfinylhydrazides, extended pi-conjugation adds a sulfide-like resonance structure that is responsible for their insensitivity toward moisture. Activation barriers for hydrolysis, where water acts as a nucleophilic reagent, decrease with increasing positive charge on the NSO sulfur atom, a finding that might prove useful as a predictive tool in the determination of the general reactivity of an N-sulfinyl compound by experimentalists.