Electrochemical Synthesis of Gold-N-Heterocyclic Carbene Complexes**

An electrochemical synthesis of gold(I)-N-heterocyclic carbene (Au-NHC) complexes has been developed. The electrochemical methodology uses only imidazolium salts, gold metal electrodes, and electricity to produce these complexes with hydrogen gas as the only by-product. This high-yielding and operationally simple procedure has been used to produce eight mononuclear and three dinuclear Au-NHC complexes. The electrochemical procedure facilitates a clean reaction with no by-products. As such, Au-NHC complexes can be directly transferred to catalytic reactions without work-up or purification. The Au-NHC complexes were produced on-demand and tested as catalysts in a vinylcyclopropanation reaction. All mononuclear Au-NHC complexes performed similarly to or better than the isolated complexes.