Nitrides, Imides, and Amides

Polynuclear metal frameworks could also assist in N—N scission. Within this category fall the so-called nitriding reactions of metals (see Section XI). The cleavage of bridging diazene or hydrazine in well-defined reactions of their complexes has not been observed. 

The preparative, structural, and bonding aspects of transition metal nitrido complexes have been reviewed in detail recently (132,179). To summarize, there are three principal preparative pathways to yield nitrido complexes and these, with examples, are outlined below. 

Ammonolysis reactions of oxo complexes with ammonia or alkali metal amides, for example, Eq. (63). 

Treatment with azido compounds, such as azide ion [Eq. (65)], halidoazide [reaction (66)], or trimethylsilylazide [reaction (67)], which is the most common nitride-forming pathway. 

An interesting, but currently unique, reaction to form W(0-tBu)3N (probably tetrameric) involves the cleavage of the tungsten-tungsten triple bond of [W2(0-tBu)fi] by alkyl nitriles as shown in Eq. (68). 

---