Dinitrogen cycle

Not surprisingly, only about 20 of the chemical elements found on Earth are used by living organisms (Chapters 3 and 8). Most of them are common elements. Rare elements are used, if at all, only at extremely low concentrations for specialized functions. An example of the latter is the use of molybdenum as an essential component of nitrogenase, the enzyme that catalyzes the fixation of elemental dinitrogen. Because they are composed of common elements, living organisms exert their most profound effects on the cycles of those elements. 

The principal mechanistic events include N-N bond formation stage, where the coordinated NO reactant is transformed into the NzO semi-product via dinitrosyl ( M-(NO)2]Z) or dinitrogen dioxide ( M-N202 Z) intermediates, depending on the nature of TMI (vide infra). Simultaneously, the primary (M Z active sites are converted into the secondary [M-0]Z active sites involved in the dioxygen formation cycle [5], The mononitrosyl complexes are usually postulated to be the key intermediate species of this step [2,5,41], whereas the mechanistic role of dinitrosyls and dinitrogen dioxide is more indistinct as yet. 

The interaction between N02 and HC is clearly located in the second cycle (Figure 5.1). Baudin [32] have detected the RNOx and showed the decomposition of RNOx to CxHyOz over an Ir/CeZr02 catalyst. The dinitrogen is formed in the third cycle and is not linked to any organic-nitro compound. 

The alternative mechanistic scenario for the protonation and reduction of end-on terminally coordinated N2 through the Schrock cycle is represented by the Chatt cycle which has been developed many years earlier (5). This system is based on Mo(0) and W(0) dinitrogen complexes with phosphine coligands (Fig. 3). As expected, the intermediates of the dinitrogen reduction scheme are very similar to those of the Schrock cycle. Moreover, a cyclic generation of NH3 from N2 has been demonstrated on the basis of this system, however, with very small yields (3,4a). In order to obtain general insight into the mechanism of the Chatt cycle we have studied most of the intermediates of Fig. 3 with... 

Fig. 8. Mo/W dinitrogen complex with the P/N ligand N,N,N, N -tetrakis-(diphenylphosphinomethyl)-2,6-diaminopyridine (pyN2P

At the cathode nitric acid is reduced to dinitrogen tetroxide and water. The dinitrogen tetroxide is cycled to the anode chamber where it is oxidized to the dinitrogen pentoxide. The anolyte product contains up to 35 wt% N2Os in nitric acid with less than 1 wt% N204. 

Investigations into the mechanism of this reaction revealed several interesting facts (61). Compelling evidence was presented that a discreet Cu nitrenoid was involved in the catalytic cycle. Photolysis of a solution of tosyl azide and styrene in the presence of the catalyst afforded aziridine with the same enantioselectivity as obtained from the PhI=NTs reaction, Eq. 69. Since photolysis of tosyl azide is known to extrude dinitrogen and form the free nitrene, the authors argue that this is indicative of a common Cu-nitrenoid intermediate in this reaction. 

A series of model studies initiated in the early 1960s by the groups of Chatt and Hidai demonstrated that dinitrogen could be bound and reduced to ammonia at a single metal centre by Mo and W complexes (Chatt et al., 1978 Hidai, 1999). However, although examples of virtually all the proposed intermediates in a Chatt cycle were isolated, no catalytic reduction of N2 to NH3 was ever achieved. Catalytic reduction of dinitrogen to ammonia... 

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