Copper triamine complexes

The same type of Au- -N interaction between adjacent [Au(CN)4] anions is found in [Cu(dien)][Au(CN)4]2 and [Cu(en)2][Au(CN)4]2 (dien = diethylenetriamine en = ethylenediamine) [48], although in these examples the copper cations act as bridges between neighboring chains generating 2-D sheets, as shown in Figure 5.26. The Au- -N separations, of 3.001 and 3.137 A in the triamine complex and 3.035(8) A in the diamine one are similar to those in other tetracyanoaurate(III) derivatives. Additional weak hydrogen bonds between amino hydrogen and N(cyano) atoms increase the dimensionality of the supramolecular structure. 

Recently, Bunton et al. synthesized the Ci6H33-attached triamine copper(II) complex 8b [26], which promoted the hydrolysis of diphenyl 4-nitrophenyl phosphate (DNP) at alkaline pH. The catalytic activity was almost the same as that for Menger s previously reported comicellar system with 3b. The active species was proposed to be the hydroxide-bound copper(II) complex 8b. The pvalue of the copper(II)-bound water molecule was speculated to be about 8 from the fact that the nonalkylated and tetradecyl homologous copper(II) complexes have a pvalue of 8 (determined by DNP hydrolysis kinetics). Since the micellar metal complex 8b was not fully characterized either in the solid state or in a micellar solution, its hydrolysis mechanism remains to be elucidated. 

Thus, polydispersities decrease with conversion, p, with the rate constant of deactivation, k, and with the eoneentration of deactivator, [X-Cu(II)], however, they increase with the propagation rate eonstant, kp, and the concentration of initiator, [RX] . This means that more uniform polymers are obtained at higher conversions, when the concentration of deactivator in solution is high and the eoneentration of initiator is low. Also, more uniform polymers are formed when the deaetivator is very reactive (e.g., copper(II) complexed by bipyridine or triamine) and monomer propagates slowly (e.g., styrene rather than acrylate). 

A third driving force for the observed selectivity, complementing and amplifying copper s choice of the methylated aldehyde, is the preference of iron(II) to incorporate the nonmethylated aldehyde into complexes of type 14. As shown in Scheme 1.16, the addition of iron(II) to a mixture of triamine and both aldehydes gave a product mixture in which nonmethylated and methylated aldehydes are present in a 3 97 ratio following equilibration. Only the two products shown in Scheme 1.16 were observed in the product mixture. The reaction of Scheme 1.16 thus deviates substantially from a statistical mixture of products indeed, only two of the expected four products are observed to form. No evidence was found of complexes incorporating two or three equivalents of methylated aldehyde. 

We have prepared a variety of new Schiff base bis crown ether ligands (98-100) that contain alkali and transition metal coordinating sites via the condensation of two or three equivalents of 4-formyl-benzo-15-crown-5 with an appropriate di- or triamine (Scheme 18). Homometallic copper(I), silver(I), and heteropolymetallic copper(I)-sodium, silver-(I)-sodium, and potassium complexes have been isolated. The singlecrystal X-ray structure of the [Cu(57)K](PF6)2 complex (100) is shown... 

In the presence or absence of a copper catalyst, O-arylation of alcohols and phenols by Ph3Bi(OAc)2 proceeds to give the corresponding aryl ethers.196-198 The monophenylation of m-l,2-cyclopentanediol with Ph3Bi(OAc)2 in the presence of a Cu(n) complex bearing a chiral triamine or diamine ligand affords an a-hydroxy phenyl ether with moderate enantiomeric excesses up to 38% (Equation (127)).199 The copper-catalyzed O-arylation has been success-fully applied to the synthesis of immunosuppressive macrolides. 

Bearing this in mind, we designed and synthesized a number of P-CD derivatives [27-34] which could i) bind copper(II) forming a multisite recognition system ii) show thermodynamic stereoselectivity in copper(II) ternary complexes iii) perform chiral separation of unmodified amino acid enantiomers. Among the monofunctionalized P-CD derivatives, only those functionalized in position 6 with diamines show chiral molecular recognition [29,32,35-37]. On the contrary, the P-CDs both functionalized in position 3 and those where a triamine was attached to the narrower rim of the toroid do not act as chiral receptors. 2-(aminomethyl)pyridine, histamine and NH3 molecules were used to obtain the three isomers of P-CDs (Figure 3), but only the A,BCD-NH2 molecule, coordinated to the copper(II) ion, is seen to have enatioselective effects on aromatic amino acids [38]. 

In the case of aliphatic triamines, (1-1-1) template condensation can be achieved if the number of atoms separating terminal NH2 groups equals 7. Thus, by interaction of dipropylenetriamine with dap on manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) matrices, it is possible to synthesise the 14-membered macrocyclic ligand L695 as appropriate complexes (Eq. 3.30) [71, 72, 74-76]. 

When dap reacts with an aromatic 3,3-triamine in the presence of nickel(II), copper(II) or cobalt(II) perchlorate in ethanol, macrocyclic complexes with tetra-dentate ligands [M(L712)](C104)2 and having octahedral structures are isolated (Eq. 3.35) [73]. 

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