One-Pot Synthesis and Unpredicted Hydrogen Bonds of the Guanidinium Triflates from Readily Available Amines, Carbodiimides, and Zn(OTf)₂

The first synthesis of trisubstituted guanidinium triflates has been achieved by a simple one-step procedure from readily available amines, carbodiimides, and Zn(OTf)₂. X-ray analysis revealed they adopt 1-D chain-like or novel 3-D hydrogen-bonded networks, which have not been reported previously in the solid structure of guanidinium salts. Isolation of a binuclear zinc complex and its subsequent carbodiimide insertion provide the insight into the mechanism for the formation of guanidinium triflates.