Dinitrogen sulfide

C. Wenti up and P. Kamhouris, N-Sulfides Dinitrogen Sulfide, Thiofulminic Acid and Nitrile Sulfides, Chem. Rev., 91, 363 (1991). 

However, all attempts to demonstrate the formation of dinitrogen sulfide (29) by mass spectrometry in gas-phase pyrolysis failed and since dinitrogen sulfide (erroneously) had been reported <75CPL(33)393> to be a Stable compound at RT Equation (1) was excluded <78JOC48l6>. Holm et al. stated that the thioacyl azide may exist as two conformers E (31) and Z (32)) (Scheme 3) <78JOC48i6> where the rotation around the C—N bond is believed to be restricted because of a partial doublebond character. 

As an overall conclusion two routes seem to operate in the thermal degradation of 1,2,3,4-thiatriazoles a major route leading to nitrile (28) and dinitrogen sulfide (29) (Equation (1)), and another leading to isothiocyanate (27) most likely via thioacyl azide (24) from the Z-form (32) and presumably accompanied by formation of nitrile (28) from the -form (31). 

The mechanism of the decomposition reaction of 5-methoxy- 1,2,3,4-thiatriazole to dinitrogen sulfide and methoxy-nitrile was studied by the DFT method at the CCSD(T)//MP2/6-31+G level of theory <2003JOC6049>. The calculations indicated that this is a concerted retro-[2+3]-dipolar cycloaddition process with an activation energy of 28.9 kcal mol 1 and a reaction energy of 1.9 kcal mol. This unimolecular decomposition is favored due to the entropy gain (25.8 eu) involved in the overall reaction (Scheme 1 and Table 2). 

Table 2 Calculated data for the activation and reaction energy in kcal mol 1 for the thermal decomposition of 5-methoxy-1,2,3,4-thiatriazole to dinitrogen sulfide and methoxycarbonitrile...

Theoretical method 5-Methoxy-l,2,3,4-thiatriazole Transition state Dinitrogen sulfide methoxycarbonitrile... 

Dimethyl sulfide [Methane, thiobis-], 16 Dinitrogen tetroxide [Nitrogen oxide (Na 04)], 65 Disulfide, dimethyl-, 9... 

D.6 Write the formula of (a) dinitrogen tetroxide (b) hydrogen sulfide (c) dichlorine heptoxide (d) nitrogen triiodide (e) sulfur dioxide (f) hydrogen fluoride (g) diiodine hexachloride. 

Dimroth reflux condenser, 59, 20 Dimsyl anion, 55, 18 Dineopentyl sulfides, 58,146 Dinitrogen tetroxide, 56, 65... 

Immediate ignition in the gas phase occurs with ammonia, dinitrogen oxide or hydrogen sulfide. 

The solid produced by interaction of phospham and hydrogen sulfide at red heat is probably a trimeric triphosphatriazine such as phospham. The solid ignites in slightly warm air or in dinitrogen tetraoxide, and is violently oxidised by nitric acid. 

Sulfides Sulfur Sulfur dioxide Sulfuric acid Sulfuryl dichloride Acids, powerful oxidizers, moisture Oxidizing materials, halogens Halogens, metal oxides, polymeric tubing, potassium chlorate, sodium hydride Chlorates, metals, HC1, organic materials, perchlorates, permanganates, water Alkalis, diethyl ether, dimethylsulfoxide, dinitrogen tetroxide, lead dioxide, phosphorus... 

A new representative of a multicopper cluster in a protein is Cuz in nitrous oxide reductase. As was discussed above this enzyme contains a binuclear CuA centre as in COX. While the latter in addition has CuB in the form of a copper-heme group, N20 reductase has Cuz which is the site of dinitrogen formation from the substrate N20. Recently a central inorganic sulfide has been found as a ligand to copper and multiple forms of Cuz were detected in the enzyme from Paracoccus pantotrophus.134 More recently a tetranuclear copper cluster with X-S bridges was proposed as structure for Cuz..135... 

One of the enzymes given in Table 23 is nitrogenase, which is responsible for the fixation of dinitrogen to give ammonia. Molybdenum probably serves as the binding site for N2, and is present in the iron-molybdenum cofactor, which is a molybdenum-iron sulfide cluster. Nitrogenase will be considered in Section 63.1.14, which deals with the nitrogen cycle. 

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