Protic pyrazoles (N-unsubstituted pyrazoles) have been versatile ligands in various fields, such as materials chemistry and homogeneous catalysis, owing to their proton-responsive nature. This review provides an overview of the reactivities of protic pyrazole complexes. The coordination chemistry of pincer-type 2,6-bis(1H-pyrazol-3-yl)pyridines is first surveyed as a class of compounds for which significant advances have made in the last decade. The stoichiometric reactivities of protic pyrazole complexes with inorganic nitrogenous compounds are then described, which possibly relates to the inorganic nitrogen cycle in nature. The last part of this article is devoted to outlining the catalytic application of protic pyrazole complexes, emphasizing the mechanistic aspect. The role of the NH group in the protic pyrazole ligand and resulting metal-ligand cooperation in these transformations are discussed.
Keywords: bifunctional catalysis; homogeneous catalysis; hydrazine; metal–ligand cooperation; pincer ligand; pyrazolato; pyrazole; transfer hydrogenation.