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Reactivity of Dinitrogen Bound to Mid‐ and Late‐Transition‐Metal Centers
Author(s) -
Khoenkhoen Nitesh,
de Bruin Bas,
Reek Joost N. H.,
Dzik Wojciech I.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403041
Subject(s) - chemistry , electrophile , transition metal , catalysis , manganese , rhenium , reactivity (psychology) , molybdenum , homolysis , disproportionation , inorganic chemistry , reductive elimination , radical , photochemistry , organic chemistry , medicine , alternative medicine , pathology
This review presents a comprehensive overview of the reactions of N 2 within the coordination sphere of transition metals of groups 6 to 9. Many of these metals mediate the reaction of N 2 with protons under reductive conditions, which can lead to the (catalytic) formation of ammonia or hydrazine, and the mechanisms of these reactions somewhat resemble the mode of action of nitrogenase enzymes. Alternatively, coordinated N 2 can react with carbon and silicon electrophiles and radicals to allow, for example, the catalytic formation of silylamines. Another approach in N 2 activation involves the homolytic splitting of dinitrogen to form intermediate nitrides in analogy to the Haber–Bosch process. Thus formed nitrides can undergo follow‐up reactions with protons or carbon electrophiles. Molybdenum, tungsten, and iron reveal the richest chemistry of coordinated N 2 ; however, chromium, manganese, rhenium, osmium, and cobalt systems provide alternative pathways in the making and breaking of bonds on the dinitrogen molecule.