Nitrido Complexes of Transition Metals

Abstract

Abstract In the past decade new syntheses and numerous structural determinations have enlivened studies in the still relatively young field of nitrido‐transition‐metal complexes. Aside from the terminal function of the nitrido ligand MN:, this group also occurs as linear μ 2 ‐bridging ligand in symmetric and asymmetric coordination; examples are known with almost right‐angled bridge function; and, finally, it also functions as μ 3 ‐bridging ligand. Accordingly, the fresh impulses given to synthetic chemistry by nitrido complexes are also many‐sided: such complexes are used, inter alia, for the preparation of phosphaniminato and thionitrosyl complexes as well as for the synthesis of metallaheterocycles of the type MN 3 S 2 and MN 3 P 2 with delocalized π‐systems. In technetium chemistry complexes with terminal nitrido group are employed as radiopharmaceuticals, and, owing to the strong trans influence of the MN: group, nitrido complexes of molybdenum are suitable as catalysts in olefin metathesis. Finally, nitrido complexes are also of wide interest in theoretical studies.