Copper-macrocycle complex

As already mentioned, the macrocyclic ring can be further enhanced if the propylene moiety is substituted by a butylene group. Visible spectral data of a series of related compounds [Cu(L BF2)D]X 132 and the structural study of the derivative with D = H2O show that the seven-membered chelate ring influences the structure and other properties like electronic absorption of the copper(II) complex [193]. 

From this perspective they reported the structure (complex (791) Cu-Cu 10.061 A) of a m-xylyl-based TACN ligand.583 Structures of four mononuclear copper(I) complexes ((792)-(795)), supported by tridentate macrocycle, were also reported by this group. They investigated their oxygenation behavior and in each case clean formation of side-on peroxo-dicopper(II) species was demonstrated.416... 

Using 1,4,8,11-tetraazacyclotetradecane, the structure of complex (800) (distorted trigonal planar Cu-Cu 6.739 A) was determined. Reactivity with 02 was investigated to demonstrate the formation of trans-l,2-peroxo species.585 As part of their work with copper(I) complexes with 02, the structure of a dicopper(I) complex ((801) distorted tetrahedral 7.04 A), supported by macrocyclic ligand environment, was reported by Comba and co-workers. Tolman and co-workers structurally characterized a three-coordinate copper(I)-phenoxide complex (802) (planar T-shaped) that models the reduced form of GO.587 The copper(I) analogue [Cu(L)][CF3-SO3]-0.43MeOI I (803) of a copper(II) complex (534) was also reported to demonstrate the role of ligand framework conformability in CV /Cu1 redox potentials.434 Wilson and co-workers... 

M(iii) and Cn(m) complexes. In early classic studies the redox chemistry of tetraaza macrocyclic complexes of Ni(n) and Cu(n) (of the Curtis and reduced Curtis type) was investigated in acetonitrile (Olson Vasilevskis, 1969 1971). These authors were the first to report the electrochemical generation of Ni(m) and Cu(m) complexes of such N4-cyclic ligands. Since this time, a considerable number of related studies, involving both nickel and copper macrocyclic species, have been reported. 

The use of a lipophilic zinc(II) macrocycle complex, 1-hexadecyl-1,4,7,10-tetraazacyclododecane, to catalyze hydrolysis of lipophilic esters, both phosphate and carboxy (425), links this Section to the previous Section. Here, and in studies of the catalysis of hydrolysis of 4-nitrophenyl acetate by the Zn2+ and Co2+ complexes of tris(4,5-di-n-propyl-2 -imidazolyl)phosphine (426) and of a phosphate triester, a phos-phonate diester, and O-isopropyl methylfluorophosphonate (Sarin) by [Cu(A(A(A/,-trimethyl-A/,-tetradecylethylenediamine)l (427), various micellar effects have been brought into play. Catalysis of carboxylic ester hydrolysis is more effectively catalyzed by A"-methylimidazole-functionalized gold nanoparticles than by micellar catalysis (428). Other reports on mechanisms of metal-assisted carboxy ester hydrolyses deal with copper(II) (429), zinc(II) (430,431), and palladium(II) (432). 

DR. RALPH WILKINS (New Mexico State University) What is the rate of the reaction of trien with your copper macrocyclic tetrapeptide complex Based on your mechanism it should be... 

E. L. Hegg, J. N. Burstyn, Hydrolysis of Unactivated Peptide Bonds by a Macrocyclic Copper(II) Complex Cu([9]aneN3)Cl2 Hydrolyzes Both Dipeptides and Proteins , J. Am. Chem. Soc. 1995, 117, 7015-7016. 

Copper(I) complexes can be generated by radical reduction of the corresponding Cu(II) complex. A few copper(I) macrocycles are remarkably stable but usually they are strong reducing agents reactive in O2, and disproportionate to copper(II) and metallic copper. 

Much more pronounced is the macrocyclic or [l]-cryptate effect found in 10 as compared with 2 the stability constant for K+ complexation increases by about 104 (in methanol) on ring formation. A similar increase has been observed between copper-(II) complexes of acyclic and macro-cyclic tetra-aza ligands (139). 

The redox properties of the copper(II) ion in saturated polyaza macrocyclic complexes CuN4 and CuNj have been shown1020 to vary with the chelate ring size, and the very negative E° values (Figure 62) are consistent with a macrocyclic effect , from stability constant measurements.976... 

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