Research inspired by the chemistry of nitrogenase — Novel metal complexes and their reactivity toward dinitrogen, nitriles, and alkynes

Summarized here are our continuous studies of the last three decades concerning syntheses of new types of complexes learned from nitrogenase and their reactivites toward dinitrogen, nitriles, and alkynes. For Mo and W dinitrogen complexes with tertiary phosphine coligands, a variety of their intriguing reactivities have been demonstrated, and novel transformations of the N2 ligands into numerous nitrogen-containing ligands and compounds have been developed. The C≡N bond cleavage of certain nitriles also proceeds on the Mo site surrounded by tertiary phosphines. Stimulated by the sophisticated structure of the active site of nitrogenase, multinuclear metal–sulfur complexes have been synthesized in rational ways. New types of stoichiometric and catalytic reactions of alkynes have been found by using the thiolato-bridged diruthenium complexes and some cubane-type sulfido clusters containing a noble metal.Key words: nitrogen fixation, molybdenum and tungsten dinitrogen complexes, ruthenium thiolato complexes, metal sulfido clusters, nitriles, alkynes.