Dinitrogen dioxide

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. 

Complexes of N-N bonded dinitrogen dioxide, such as depicted in pathway B of Scheme 5, would appear to be necessary in order to effect the formation of the N-N bond. This has been treated theoretically as a metal promoted reductive coupling of 2 NO to form a hyponitrite complex (79). The Cu Tp112) system was also shown to catalyze NO oxidations of benzyl and isopropyl alcohol to benzaldehyde and acetone (Eq. (37)). Electrospray mass spectrometry indicated that higher... 

Dinitrogen Dioxide.—Crystals of nitric oxide10 contain its dimer,... 

This structure should be contrasted with an alternative formulation of this species as a complex containing one linear and one bent nitrosyl which is suggested in (110) for the Ru analog. The dinitrogen dioxide ligand differs... 

Trisulfur dinitrogen dioxide or bis(sulfinylimino) sulfide, S(XSO)2, is a yellow, moisture-sensitive solid that has been known since 1953. It is conveniently prepared in high yields by the procedure described in equation (17). 

Consider N2O3. This is a binary molecular compound, as you would predict because N and O are nomnetals. According to Rule 1, you name it afto the elements, N before O, following the order of elements in the formula. By Rule 2, the N is named exactly as the element (nitrogen), and by Rule 3, the O is named as the anion (oxide). The compound is a nitrogen oxide. Finally, you add prefixes to denote the subscripts in the formula (Rule 4). As Table 2.7 shows, the prefix for two is di-, and the prefix for three is tri-. The name of the compound is dinitrogen dioxide. 

Structure and Stability of Asymmetric Dinitrogen Dioxide (a-NzOi). 

The authors postulated a reaction mechanism involving an O-atom transfer from a coordinated NO to the neighboring CO, followed by an intramolecular attack of the second coordinated NO group on the Ir-N system, invoking a ni-trene [94] intermediate. However, follow-up studies employing isotopically labeled NO ( NO) mled out this nitrene intermediate possibihty and provided evidence for dinitrogen dioxide (N2O2) as the reactive intermediate which transfers an O-atom to CO [90, 95, 96). 

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