Solvothermal in Situ Metal/Ligand Reactions:  A New Bridge between Coordination Chemistry and Organic Synthetic Chemistry

Several important solvothermal (including hydrothermal) in situ metal/ligand reactions and their mechanisms, including dehydrogenative carbon-carbon coupling, hydroxylation of aromatic rings, cycloaddition of organic nitriles with azide and ammonia, transformation of inorganic and organic sulfur, as well as the CuII to CuI reduction, are outlined in this Account. The current progress clearly demonstrates the important potential of such reactions in the crystal engineering of functional coordination compounds and one-pot synthesis of some unusual organic ligands that are inaccessible or not easily obtainable via conventional methods, thereby substantiating our expectation that a new bridge has been created between coordination chemistry and synthetic organic chemistry.