Copper trivalent, compounds

Intermediates such as 224 resulting from the nudeophilic addition of C,H-acidic compounds to allenyl ketones such as 222 do not only yield simple addition products such as 225 by proton transfer (Scheme 7.34) [259]. If the C,H-acidic compound contains at least one carbonyl group, a ring dosure is also possible to give pyran derivatives such as 226. The reaction of a similar allenyl ketone with dimethyl mal-onate, methyl acetoacetate or methyl cyanoacetate leads to a-pyrones by an analogous route however, the yields are low (20-32%) [260], The formation of oxaphos-pholenes 229 from ketones 227 and trivalent phosphorus compounds 228 can similarly be explained by nucleophilic attack at the central carbon atom of the allene followed by a second attack of the oxygen atom of the ketone at the phosphorus atom [261, 262], Treatment of the allenic ester 230 with copper(I) chloride and tributyltin hydride in N-methylpyrrolidone (NMP) affords the cephalosporin derivative 232 [263], The authors postulated a Michael addition of copper(I) hydride to the electron-... 

Since isolable organocopper) 11) compounds do not apparently exist, it is rather surprising that oxidation of the cuprate CdI+[(CF3)2Cu ] (prepared in situ) with thiuram disulfide affords (CF3)2Cu "S2CNEt2 (see Eqn. 1 in Scheme 1.6), the first and so far only example of an organocopper compound with the copper atom in the trivalent oxidation state. The structure of this compound was unambiguously proven by an X-ray crystal structure determination (see Fig. 1.2) [37]. 

It is well established that metallic copper or copper salts efficiently catalyze N- and O-arylation reaction using pentavalent and trivalent organobismuth compounds [5-9, 24]. The C-arylation reaction of phenols and active methylene compounds using pentavalent organobismuth compounds are usually mediated by a base. However, in some cases, copper catalysts mediate C-arylation using pentavalent organobismuth compounds. 

Fluoroalkyl copper compounds, 17 143, 144 a-Fluoroalkylidinehydrazines, 33 167 2-Fluoroalky 1 -2 phospha-1,3-dialky 1 -1,3-diaze-tidinones, synthesis of, 14 87 Fluoroanions, trivalent, uranium, 34 94—95 Fluoroantimony compounds, 7 17 Huoroaryl copper compounds, 17 143, 144 Fluoroberyllates anhydrous, 14 267-276 aqueous chemistry of, 14 274-278 glasses, 14 265-267 preparation and properties of, 14 265-267... 

It was pointed out by Hume-Rothcry 4 in 1926 that certain interns etallic compounds with close]y related structures but apparently unrelated stoichiometric composition can be considered to have the same ratio of number of valence electron to number of. atoms,. For example, the j8 phases of the systems Cu—Zti, Cu—-Alv and Ou -Sn are analogous in structure, all being based on the -4.5 arrangement their compositions correspond closely to the formulas CuZn, CusAl, and CtttSn. Considering copper to be univalent, zinc bivalent, aluminum trivalent, and tin quadrivalent, we see that the ratio of valence electrons to atoms has the value f for each of these compounds ... 

The types of compounds formed by gold(I) and gold(III) often differ from those of other metals due to the constraints imposed by coordination number and electron count at the metal. Thus, for example, whereas 7r-bonded cyclopentadienyl complexes of palladium and platinum are numerous (336), and a copper(I) species of this type is known (337), cyclopentadienyl complexes of univalent (94, 96, 97) and trivalent (228) gold have invariably been found to be fluxional behavior, similar to that in dicyclopentadienylmercury, was involved (228). 

Soai [8], Bolm [9], Feringa [10], and Alexakis [11] have reported nickel-or copper-catalyzed asymmetric conjugate addition of diethylzinc, with chiral amino alcohols or a chiral trivalent phosphorus compound (Scheme 8D.2). 

The bivalent metals, as usual, combine with two molecules of biguanide to form 4-coordinated planar complexes, while the trivalent cobalt and chromium combine with three molecules of the ligand to produce a 6-coordinated octahedral configuration. The only exception is the trivalent silver which yields, however, a 4-coordinated planar complex. The preparation of the free tris(biguanidato) chromium, Cr(C2N5H6)s, in the anhydrous state,6 as well as of the corresponding anhydrous cobalt(III),8 copper(II), cobalt(II), palladium(II), and nickel(II) compounds, provides indisputable evidence for the structure proposed. Similar anhydrous metallic complexes with numerous substituted biguanides also have been included in the above-mentioned studies. 

Bleomycin Bleomycin is incompatible and loses its potency if it is administered with solutions of benzylpenicillin sodium, carbenicillin, cephazolin or cephalothin sodium, hydrocortisone sodium succinate, mitomycin, methotrexate, nafcillin sodium, aminophylline, ascorbic acid, terbutaline, divalent and trivalent cations (especially copper), compounds containing sulfhydryl groups, and precipitation by hydrophobic anions, essential amino acids, riboflavine, dexamethasone, and frusemide. 

The stabilities of the oxidation states within this series are disturbingly free from trends. For copper, the +2 state predominates for silver, the + 1 state is most important finally, of the known gold compounds for which a valence state of the metal may be easily assigned, most contain trivalent gold. At higher temperatures, the cuprous state of copper becomes more important than the cupric. 

Barton, D. H. R., Finet, J. P., Khamsi, J. Copper salt catalysis of N-phenylation of amines by trivalent organobismuth compounds. Tetrahedron Lett. 1987, 28, 887-890. 

Pyrazolin-5-ones form complexes with both inorganic and organic compounds much more readily than do the 2-pyrazolin-5-ones. The most extensive series of complexes is that formed with a variety of metallic salts. Antipyrine (2,3-dimethyl-l-phenyl-3-pyrazolin-5-one) forms a series of complexes with salts of divalent, trivalent and tetra-valent metals. Two molecules of antipyrine form a complex with one molecule of copper, cadmium, cobalt and zinc salts.266,866,1116 Complexes prepared from metallic nitrates are usually hydrated.1322 There also exists a series of complexes in which three molecules of antipyrine form a complex with one or two molecules of metallic salts. Such complexes form with two molecules of simple ferric salts272 or with one of complex iron cyanides.608 Nitrates of thorium, lanthanum, cerium and samarium also give such complexes.841 This ratio also occurs in some antipyrine complexes with cadmium and zinc thiocyanate.266 A number of salts of rare earths and iron which have complex anions such as thiosulfate, thiocyanate, dithionic acid and complex iron cyanides form complexes in which six molecules of antipyrine are present.405,408 608,841,950 Stannic chloride forms salts containing three or four molecules of antipyrine and hydrochloric acid.46... 

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