Argentate(I) and (III) complexes as intermediates in silver-mediated cross-coupling reactions

Despite the potential of silver to mediate synthetically valuable cross-coupling reactions, the operating mechanisms have remained unknown. Here, we use a combination of rapid-injection NMR spectroscopy, electrospray-ionization mass spectrometry, and quantum chemical calculations to demonstrate that these transformations involve argentate(I) and (III) complexes as key intermediates.