Copper, tris amine

The [Cr(en)3]2+ and [Cr(pn)3]2+ salts have reflectance spectra (Table 11) resembling those of the hexaammines, and the six N donor atoms are assumed to complete tetragonally distorted octahedra around the metal. Stability constant measurements (Table 39) have shown that the ions [Cr(en)(aq)]2+ (vmax= 18 300 cm-1, e = 25 dm3 mol-1 cm-1) and [Cr(en)2(aq)]2+ (vma = 17 500 cm-1, e = 17 dm3 mol-1 cm-1) exist in aqueous solution, but that, as in the copper(II) system, the third ethylenediamine molecule is only weakly bound, and care is needed to prevent loss of en from tris(amine) complexes in the preparations. Several bis(amine) complexes, e.g. [CrBr2(en)2], have been isolated, and these are assigned trans structures because of IR spectral resemblances to the corresponding oopper(II) complexes. Since the spectrum of [Cr(S04)(en)2] also shows the presence of bidentate sulfate, this is assigned a trans octahedral structure with bridging anions. 

To provide a model for nitrite reductases72 Karlin and co-workers characterized a nitrite-bound complex (226) (r = 0.05)214 In an endeavor to model nitrite reductase activity, Tanaka and co-workers prepared a few mononuclear complexes (227) (r = 0.74)215 (228) (r = 0.82),216 (229) (r = 0.97),217 (230) (r = 0.16),217 (231) (r = 0.07),217 and (232) (r = 0.43 and r = 0.53)217 and studied the electrochemical reduction of N02A As a part of their activity on modeling heme-copper terminal oxidases, Holm and co-workers prepared complex (233) (r = 0.96).218 Using a sterically hindered tris(pyridylmethyl)amine, Canary et al. prepared a complex (234) (r=1.00), studied its redox behavior, and discussed various factors that may contribute to the difference (higher potential for the new complex) in the redox potential of a Cu Cu1 couple between substituted and unsubstituted ligands.2 9... 

Partial hydrolysis of a potentially heptadentate Schiff-base tripodal ligand derived from tris-(2-aminoethyl)amine and 2-hydroxyacetophenone, induced by copper(II) salts, was reported and the final copper(II) complex (377) was characterized.333 Using salicylaldehyde as a co-ligand, with a copper(II) complex (378), catalytic epoxidation was demonstrated 334... 

Calixarenes, when in their cone-conformation (54), represent versatile host systems for metalated container molecules and many examples have been reported in the literature (55-61). Reinaud and coworkers have carried out extensive work concerned with calix[6]arenes that are functionalized at the small rim by nitrogen arms (62), aiming to reproduce the hydro-phobic binding site of mononuclear zinc and copper metalloen-zymes. A recent example is the calix[6]arene ligand L1 (Fig. 3), in which a tris(2-methylpyridyl)amine unit covalently caps the calixarene small rim (63). The ligand forms copper complexes of... 

The identification of different carbonate binding modes in copper(II) and in zinc(II)/2,2 -bipyridine or tris(2-aminoethyl)amine/(bi)carbonate systems, specifically the characterization by X-ray diffraction techniques of both r)1 and r 2 isomers of [Cu(phen)2(HC03)]+ in their respective perchlorate salts, supports theories of the mechanism of action of carbonic anhydrase which invoke intramolecular proton transfer and thus participation by r)1 and by r 2 bicarbonate (55,318). 

In a related observation, reported by Tanaka et al. (81), the copper(II) complex Cu(tpa)2+ (tpa = tris[(2-pyridyl)methyl] amine) was shown to serve as a catalyst for the electrochemical reduction of nitrite to N20 and traces of NO in aqueous solution. NO and/or a copper nitrosyl complex would appear to be the likely intermediates in this process (81a). 

Aromatic amines RNH2 (R = Ph, 2-MeCgH4 or 4-MeOCgH4) are phenylated by triphenylbismuth in the presence of 0.5 equivalent of copper(II) acetate to yield diarylamines RNHPh. Butylamine yields a mixture of TV-butylaniline and N-butyldiphenylamine in this reaction and piperidine gives TV-phenylpiperidine36. A similar alkylation of the secondary amines pyrrolidine, piperidine and morpholine with trimethylbismuth or tris(2-phenylethyl)bismuth in the presence of copper(II) acetate affords tertiary amines, e.g. 14. The reaction proceeds by way of transient pentavalent bismuth compounds37. 

MCjSO solution Hibbert (1974) Protonated amine salt with magnesium tristhexafluoro-acetylacetonate) (Truter and Vickery, 1972) CFjCOOH solution (Alder el al., 1968) Altman el al. (1978) Protonated amine salt with copper(ll) tris(hexafluoroacetylacetonate) (Truter and Vickery, 1972) Hydrobromide salt (Pyzalka el al., 1983) Staab el al. (1983) Staab el al. (1988a) Saupe ei al. (1986) Staab and Saupe (1988) Staab el al. (1988b) "Zirnstein and Staab (1987). 

Another approach for the synthesis of networks relies on the polycondensation of multifunctionalized polyesters with the appropriate multifunctionalized agent, provided that one of the partner is at least tri-functionalized. Toward this end, several reaction have been reported, such as the Michael addition of amines onto acrylates [184], the coupling of ketones and oxyamines [185], the click copper(II)-catalyzed azide-alkyne cycloaddition [186], and esterification reactions [25, 159, 187]. Interestingly, if esterification reactions are used, the crosslinks are then degradable. 

A similar technique was used by Soliman, who also used a silica gel matrix and a covalent linker to tie to a series of amines, mono-, di-, tri-, and tetra-amine [15]. Using a batch equilibrium technique, he measured the removal capacities (mmole/g) for divalent forms of cobalt, nickel, copper, zinc, cadmium, and lead. In general maximum removal values (at optimum pH values) were obtained for the tetra-amine species. 

F. HEXAKIS CYANO(TRIS(2-AMINOETHYL)AMINE)COPPER(II) -CHROMIUM(III) NONAPERCHLORATE HYDRATE, [ Cu(tren)(CN) 6Cr][C104]9 H2O... 

C6Hi4Cl2N202Pt, Platinum(ll), cw-dichlorobis-(propanoneoxime)-, 34 82 C6Hi4Cl2N202Pt, Platinumfll), trani-dichloro-bis(propanoneoxime)-, 34 83 C6H18N4, tren, Tris(2-aminoethyl)amine, complex with copper(II), 34 138 CfiNNaOsW, Tungstate(O), pentacarbonylcyano-, sodium, 34 162... 

C42H logClgCrCugN30O36 H2O, Chromium, hexakis cyano(tris(2-aminoethyl)amine)-copper(II) -, nonaperchlorate, hydrate, 34 138... 

ClNa60i9P2RhS6C37H24, Rhodate(6-), trans-carbonylchlorobis(tris(3-sulfonatophenyl)-phosphine)-, sodium, 34 124 CI2B2N2C4H12, Diborane(4), 1,2-dichloro-1,2-bis(dimethylamino)-, 34 3 CI2CUN4O9C18H20, Copper(II), aquatris(2-pyri-dylmethyl)amine-, perchlorate, 34 135 Cl2Fe7N24Oi2Ci32Hi50 6H2O, Iron(II), hexa-kis cyanobis(3-salicylidenoaminopropyl)-methylamineiron(lll) -, chloride, hexahy-drate, 34 143... 

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