Copper complexes azides

Dimethyl sulphoxide (amounting to slightly more than equimolar with azide and less than 1% overall concentration in solution in methanol) accelerates the copper-catalyzed decomposition and the only product formed (97%) is the sulphoximine (21). Even in the absence of copper, DMSO and benzenesulphonyl azide were found to undergo a slow reaction in boiling methanol to give 21 (< 40%). It was suggested33) that the sulphonyl azide itself (slow) or the copper complex 24 (fast)... 

Addition of carbethoxynitrenes to olefinic double bonds occurs readily. Addition of both the singlet and the triplet species can take place, the former stereospecifically, the latter not 49>. Additions of sulphonyl nitrenes to double bonds have not been demonstrated except in two instances in which metals were present. The reason is that either addition of the starting sulphonyl azide to the double bond occurs to give a triazoline that loses nitrogen and yields the same aziridine as would have been obtained by the direct addition of the nitrene to the olefin, or the double bond participates in the nitrogen elimination and a free nitrene is never involved 68>. The copper-catalyzed decomposition of benzenesulphonyl azide in cyclohexene did give the aziridine 56 (15%), which was formulated as an attack by the sulphonyl nitrene-copper complex on the double bond 24>. 

Narang, K. K. et al., Synth. React, lnorg. Met.-Org. Chem., 1996, 26(4), 573 The explosive properties of a series of 5 amminecobalt(III) azides were examined in detail. Compounds were hexaamminecobalt triazide, pentaammineazidocobalt diazide, cis- and fram-tetraamminediazidocobalt azide, triamminecobalt triazide [1], A variety of hydrazine complexed azides and chloroazides of divalent metals have been prepared. Those of iron, manganese and copper could not be isolated cobalt, nickel, cadmium and zinc gave products stable at room temperature but more or less explosive on heating [2],... 

Figure 22. X-ray crystal structure ofthe di-copper complex of 62 with azide anion. ...

The 0-, M- and P-Toluidino-Diazido-Copper Complexes. (N3)2Cu.C7H7NH2 mw 254.78 N 38.49% grn-brn cryst mp, ortho-123° (explds), meta- 157-60°(explds), para- 135° (explds). Sol in ethylenediamine and acids. Prepn is by reacting Cu(II) azide with the appropriate toluidine isomer. The isomers have an impact sensy of 10cm, using a 1-kg wt Refs 1) Beil, not found 2) Gmelin, Syst Nr 60, Teil B, Lieferung 1 (1958) 3) A. Cirulis... 

Metal nitrene complexes were used in a number of C-H amination reactions (recent reviews [358, 359]). Copper ketiminate complexes react with azides to nitrene complexes, which were isolated [360]. (p-Ketiminate)copper(I) complex 262 (2.5 mol%) serves therefore as an efficient catalyst for the intermolecular C-H amination of alkylarenes, cycloalkanes, or benzaldehydes 260 using adamantyl azide 261 as the nitrogen source ig. 68) [361]. The corresponding adamantyl amines or amides 263 were isolated in 80-93% yield. Copper complex 262 forms initially a dinuclear bridged complex with 261. From this a copper nitrene complex is generated by elimination of nitrogen, which mediates the hydrogen abstraction from 260. 

In early days Alfred Nobel already replaced mercury fulminate (MF, see above), which he had introduced into blasting caps, with the safer to handle primary explosives lead azide (LA) and lead styphnate (LS) (Fig. 1.17). However, the long-term use of LA and LS has caused considerable lead contamination in military training grounds which has stimulated world-wide activities in the search for replacements that are heavy-metal free. In 2006 Huynh und Hiskey published a paper proposing iron and copper complexes of the type [cat]2[Mn(NT)4(H20)2] ([cat]+ = NH4, Na+ M = Fe, Cu NT = 5-nitrotetrazolate) as environmentally friendly, green primary explosives (Fig. 1.17) [3]. 

There are many structural studies of copper coordination compounds with azide ligands, mainly of mononuclear and binuclear copper complexes but a few also of trinuclear copper complexes. A comprehensive... 

Polymer-supported benzenesulfonyl azides have been developed as a safe diazotransfer reagent. ° These compounds, including CH2N2 and other diazoalkanes, react with metals or metal salts (copper, paUadium, and rhodium are most commonly used) to give the carbene complexes that add CRR to double bonds. Diazoketones and diazoesters with alkenes to give the cyclopropane derivative, usually with a transition-metal catalyst, such as a copper complex. The ruthenium catalyst reaction of diazoesters with an alkyne give a cyclopropene. An X-ray structure of an osmium catalyst intermediate has been determined. Electron-rich alkenes react faster than simple alkenes. ... 

Coloured copper complexes with EDTA and related reagents can be applied for determining Cu at higher concentrations. Cu has been determined as EDTA and NTA complexes by the derivative spectrophotometry [84,85]. Relatively high concentrations of Cu can be determined as the ammino complex (e = 120). Other sensitive methods are based on copper complexes with chloride (in water-acetone) and azide [86]. 

Copper(II) azide, an extremely sensitive explosive material, can be crystallized in the orthorhombic form by diffusing together solutions of CUSO4 and NaN3(5) in a solution of 1% hydrogen acetate in water [30]. Only small needle-shaped crystals have been grown by this technique. It should be mentioned that excess azide concentration in this solution must be avoided as the azide will form a soluble complex with copper ... 

Figure 17. Chain structure in complex copper(II) azides. ( ) N, (o) Cu.

Azide coordinated complexes, particularly copper complexes, have been extensively studied in recent years to try and understand the enormous variation of magnetic spin... 

Regiospecific catalytic cydoaddition of alkynes and azides using copper complexes as soluble organic catalysts enables the preparation of divalent and mul-... 

Under catalytic conditions, the reaction was independent of the alkyne concentration and second order with respect to Cu(I) (163). The first step in the suggested mechanism is the formation of a dinuclear copper complex, an intermediate species that reacts with the azide. 

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