The S-N bond remains a synthetically challenging motif for organic chemists to access. The problem arises from instability in many sulfenamide derivatives, which has led to fewer S-N bond surrogate molecules compared to their hydroxylamine (NH2OH) and hydrazine (NH2NH2) analogues. In turn, sulfenamides have often been omitted in studies regarding α-nucleophilicity. Herein, we provide factors responsible for the stability of the sulfenamide motif and provide new insights on the nucleophilic properties of sulfenamides as they relate to the α-effect.