Click Chemistry: Reactions of a Diazomethyl Anion with Unsaturated Bonds^†

Comprehensive Summary The reactions of potassium diazaphospholidinyl diazomethylide with phenylacetylene, acetonitrile, adamantyl phosphaalkyne, and styrene promptly form pyrazolide, triazolide, diazaphospholide, and pyrazolinide, respectively. The reaction mechanisms have been studied using DFT calculations. While the reactions with phenylacetylene and styrene proceed via stepwise pathways, those with acetonitrile and adamantyl phosphaalkyne follow concerted pathways. Additionally, the pyrazolide product readily undergoes N ‐functionalization, yielding methyl pyrazole, germanyl pyrazole, and copper pyrazolide complexes.