Recent research has highlighted the importance of cooperative mechanisms leading to the same carbamate and imidic acid products in the presence of excess water or isocyanate molecules. Wei and coworkers predicted at the MP2/6-311++G** level of theory that additional water molecules lower the barrier to reaction across both the N=C or C=O bonds. We present an analysis of how substituents influence the barrier to carbamate and imidic acid formation considering one catalyst water molecule, two catalyst water molecules, and one catalyst RNCO molecule. Our CCSD(T)/aug-cc-pV(T+d)Z//MP2/julcc-pV([T,Q]+d)Z + ∆CCSD(T)/6-31+G** results are a significant improvement over previous computations and allows for confident determination of the trends that manifest in the autocatalyzed energetics due to substituent effects.