Metal-NO Reduction Accompanied by N-O Cleavage

Many studies on N-O bond dissociation facilitated by a metal ion have initially been carried out employing cluster compounds, either in solution or the gas phase. In fact, a primary method to generate metal nitride (M-N) compounds is through N-O bond cleavage chemistry. Early examples of low-valent nitride dusters were prepared by using the nitrosonium ion [106]  

Several other nitrido clusters like [Fe4N(CO)i2] [107], [Fe5N(CO)i4] [107], HRu4N(CO)i2 [108], H3Ru4N(CO)ii [108], HOs4N(CO)i2 [109] and CoRu3N(CO)i2 [110] have also been reported to form from dusters containing a coordinated NO 

The synthesis of nitrido dusters by the condensation of monomeric nitrosyl complexes was first reported by Gladfelter and coworkers [111-113]  

Dahl and coworkers [116] reported molybdenum-promoted nitrosyl bond activation leading to the formation of nitrido and/or imido hgand-containing metal clusters. A solution of Mo2(r/ -C5Me5)2(CO)4 and Co(CO)3(NO) in tetrahydro-furan, upon photolysis under a slow stream of N2, gives ( / -C5Me5)3M03C02-(CO)8(/t3-NH)(/t4-N). 

it seems that CpW(0)(N-o-tolyl)(o-tolyl) and CpW(0)2(o-tolyl) are formed from CpW(NO)(o-tolyl)2 via independent pathways. 

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