Copper nitrate complexes

Mercuric halides, silver nitrate, and copper nitrates form stable complexes with bis-2.2 -thiazolylazo compounds (1591). for which the X-ray structure is not yet known. 

The ability of cobalt(II), nickel(II), and copper(II) to exhibit a greater tendency than Zn(II) towards bidentate coordination is further illustrated by structural comparisons within a series of bridging carbonate complexes (188). For example, of the complexes [TpPr 2]M 2(/x-C03) (M = Mn, Fe, Co, Ni, Cu, Zn), only the zinc derivative does not exhibit bidentate coordination at both metal centers (151,153). Furthermore, the carbonate ligand in the complexes [TpPr 2]M 2(/x-C03) (M = Mn, Fe, Co, Ni, Cu) also exhibits varying degrees of asymmetry that closely parallel the series of nitrate complexes described earlier (Fig. 47 and Table IX). 

Buffinger, D. R., et al J. Coord. Chem., 1988, 19(1-3), 197 A double salt of the nitrate and the copper(II) salt of an organometallic ligand was found to explode at around 100°C. In view of the oxidising powers of the nitrate, complexes of this nature are not likely to be stable. 

Diels-Alder reactions are one of the most famous examples which are accderated by a Lewis acid. Various water-stable Lewis adds such as Ln(OTf)3,1371 methylrhenium trioxide,1381 copper nitrate,1391 copper bis(dodecyl sulfate) (4b),1401 indium chloride,1411 and bismuth triflate1421 have been used for Diels-Alder and aza-Diels-Alder reactions in water. Furthermore, a catalytic asymmetric Dids-Alder reaction in water using a copper complex of an amino... 

Nitrotetrazole is readily prepared from the diazotization of 5-aminotetrazole in the presence of excess sodium nitrite and is best isolated as the copper salt complex with ethylenediamine. The salts of 5-nitrotetrazole have attracted interest for their initiating properties. The mercury salt is a detonating primary explosive. The amine salts of 5-nitrotetrazole are reported to form useful eutectics with ammonium nitrate. ... 

Catalysts suitable specifically for reduction of carbon-oxygen bonds are based on oxides of copper, zinc and chromium Adkins catalysts). The so-called copper chromite (which is not necessarily a stoichiometric compound) is prepared by thermal decomposition of ammonium chromate and copper nitrate [50]. Its activity and stability is improved if barium nitrate is added before the thermal decomposition [57]. Similarly prepared zinc chromite is suitable for reductions of unsaturated acids and esters to unsaturated alcohols [52]. These catalysts are used specifically for reduction of carbonyl- and carboxyl-containing compounds to alcohols. Aldehydes and ketones are reduced at 150-200° and 100-150 atm, whereas esters and acids require temperatures up to 300° and pressures up to 350 atm. Because such conditions require special equipment and because all reductions achievable with copper chromite catalysts can be accomplished by hydrides and complex hydrides the use of Adkins catalyst in the laboratory is very limited. 

When heated with nitric acid, copper(l) sulfide decomposes forming copper nitrate and hydrogen sulfide. The compound dissolves in aqueous solutions containing cyanide ions forming soluble copper-cyanide complexes. 

Copper(I) nitrate complexes with organophosphines, arsines, and stibines can be readily prepared in good yield in alcohol solution by such ligand reduction reactions.9 In the cases of the arsines and stibines, addition of copper powder... 

Another copper catalyst, prepared by treating a NaY zeolite with copper nitrate, for ammonia oxidation (160—185°C) has been studied by Williamson et al. [349], The reaction is first order in NH3 and zero order in oxygen. The mechanism here is based on a Cu(II)(NH3)4+ complex formed in the large cavities of the zeolite. The rate-determining step is the reduction of Cu(II) by ammonia. 

N-Benzylethylenediamine forms distorted octahedral CuL2X2 (X = Cl, Br, I, N03, or C104), the extent of distortion depending upon the anion [CuLX2] (X = Cl or Br) are also distorted polymeric octahedral complexes 677 The copper(n) nitrite and nitrate complexes of 1,2-dimorpholinoethane (edm) and 1,2-dipiperidinoethane,... 

N3CI plane (207). The other halids and the cadmium complexes are isomor-phous with the appropriate forms, and undoubtedly possess related five-coordinate structures. A number of studies of the vibrational spectra of the [M(terpy)X2] species have been described, all of which support the formulation as isomorphous five-coordinate complexes (124, 171, 225, 371). The copper(II) complexes [Cu(terpy)Cl2] are isostructural, and a number of studies of the paramagnetic species doped into a host matrix of [Zn(terpy)Cl2] have been reported (23, 213). The zinc complex [Zn(terpy)Cl2] exhibits absorption maxima at 22,650 and 18,000 cm (23, 348). The mercury(II) halide adducts are not so well characterized, but may be prepared by the direct reaction or HgX2 with terpy (171) or by trans-metallation of [Ph2Sn(terpy)Cl2] with HgCl2 (471). They are thought to possess similar, five-coordinate structures. The structures of the 1 1 adducts of the nitrates M(N03)2 terpy are not known with any certainty (171,328). A Cd NMR study of Cd(N03)2 terpy has been reported (430). 

There also exists a considerable number of ionic tris(thiourea) complexes. Thiourea is capable of reducing copper(II) salts to copper(I) complexes in acid solution to form [Cu(thiourea)3] salts. The following have been isolated chloride (194, 195), nitrate (194), oxalate (194, 195, 298), monohydrogen arsenate, and phosphate (298). 

Sposito G. and Holtzclaw K. M. (1979) Copper(ll) complexation by fulvic acid extracted from sewage sludge as influenced by nitrate versus perchlorate background ionic media. Soil Sci. Soc. Am. J. 43, 47-51. 

The paper discusses two types of reaction involving metal complexes, and it is postulated that each proceeds by an initial free-radical step. In reactions between metal carbonyls and N2O4—NO2 mixtures, the nature of the product depends upon the phase in which the reaction is carried out. In the liquid phase, where the predominant equilibrium is N204 N0+ + NO3-, metal nitrates or carbonyl nitrates are formed in the gas phase, where the equilibrium is N2O4 2NO2/ nitrites or their derivatives are produced. Reactions of Mn2(CO) o Fe(CO)5, Co2(CO)3, and Ni(CO)4 are discussed. Anhydrous metal nitrates in which the nitrate group is covalently bonded to the metal have enhanced reactivity. This is believed to result from the dissociation M—O—N02 M—O + NO2 This can explain the solution properties of beryllium nitrates, and the vigorous (even explosive) reaction of anhydrous copper nitrate with diethyl ether. 

This reaction occurs only under conditions in which the strong covalent bonds between copper and the nitrate groups are maintained. Copper nitrate is a covalent monomer in the gas phase (3, 47) and in solution in nonaqueous solvents (5). However, it retains its reactivity towards ether only in those solvents which are weak ligands to the copper atom. If we say for the sake of discussion that copper nitrate dissolves in basic solvents to give a complex of the type... 

Oxidation of sulfur compounds. The copper(lI) nitrate complexed with dimerizes thiols to afford disulfides and oxidizes sulfides to sulfoxides. 

Faujasite-X zeolite (NaX) (Si/Al = 1.23, ca. 2 pm particle size, from Aldrich Chemical Company), ammonium hydroxide (assay 29+%, from Fisher Chemical Company), cobalt(II) chloride (99+ % assay) and copper nitrate hydrate [Cu(N03). H20, 101.7 % by EDTA complexation, from J.T. Baker Chemical Company] were used. 

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