Copper macrocyclic ligands

A dinuclear iron(ll/Ill) complex bearing a hexadentate phenol ligand displayed moderate activity toward aziridination of alkenes with PhlNTs a large excess of alkene (2,000 equiv. vs PhlNTs) was required for good product yields (Scheme 22) [76]. It is noteworthy that complex 4 is active in the aziridination of aliphatic alkenes, affording higher product yields than copper (11) catalysts with tetradentate macrocyclic ligands [77]. 

It is to be mentioned here that the coordination chemistry of macrocyclic ligands is covered in Volume 7. Therefore only selected systems having some direct relevance to the bioinorganic chemistry of copper will be discussed. Readers are recommended to consult review articles/ 3... 

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... 

Two distinct classes of ligand have been investigated for the complexation of copper the polyfunctional bis(thiosemicarbazones) and the macrocyclic ligands exemplified by 1,4,8,11-tetraaza-... 

The macrocyclic ligands utilized for incorporation of copper generally contain four nitrogens separated by ethylene or propylene groups. The overall size of the macrocycle, thus, extends to fourteen atoms in the case of 4-[(l,4,8,ll-tetraazacyclotetradec-l-yl)methyl]benzoic acid (PCBA) (Figure 8).112... 

In the promotion of less-common oxidation states, much attention has been focused on the redox behaviour of transition metal ions such as nickel and copper although many other metal types have also had unusual oxidation states stabilized by macrocyclic ligands. However, within the limitations of a single chapter it is not possible to attempt a wide ranging... 

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 Ni(II) complex of the hexaaza macrocyclic ligand 1 is reported to show a high activity for the electrocatalytic reduction of C02 to CO when a rotating copper disc electrode is used (85). In addition, water-soluble Niu-azacyclam complexes, 3a-3g, where R = carboxamide or sulfonamide, either aliphatic or aromatic, are found to be active in the electrocatalytic reduction of C02 at a mercury cathode. The efficiency is comparable to that of [Ni(cyclam)]2+ (14). 

As shown in Eq. 19.21. it is thought that this reaciion takes place through a dimeric, bridged intermediate of coordination number 5. Copper tends lo form a maximum of five reasonably strong bonds,60 so complexation with a nonlabile tetracoordinate macrocyclic ligand (NJ provides only one additional site for a sulfur ligand. The reaction in Eq. 19-21 is inhibited, and a thiolate complex can be isolated 6 ... 

A number of the above complexes may be alternatively considered as macrocyclic ligands or compartmental ligands, but as the emphasis has been primarily in terms of the local copper(I) stereochemistry and the polynuclear nature of the complexes, they have been included above. As there is no crystallographic data on biological copper(I) systems, this section will have to await the further refinement of the structure of Panutirus Interruptus hemocyanin.353... 

Two interlocked macrocyclic ligands as in (15) are topologically related to the catenanes, whence the name catenand derives.34,186 187 These macrocycles complex a variety of metals, presumably in a tetrahedral geometry.34,186 The stabilizing effect of the catenand topology is evident in the observed redox stability of the nickel(I) complex186 as well as the reluctance toward demetallation, observed for the copper(I) complexes.187... 

Template reactions between malonaldehydes and diamines in the presence of copper(II), nickel(II) or cobalt(II) salts yield neutral macrocyclic complexes (equation 15).99-102 Both aliphatic102 and aromatic101 diamines can be used. In certain cases, non-macrocyclic intermediates can be isolated and subsequently converted into unsymmetrical macrocyclic complexes by reaction with a different diamine (Scheme ll).101 These methods are more versatile and more convenient than an earlier template reaction in which propynal replaces the malonaldehyde (equation 16).103 This latter method can also be used for the non-template synthesis of the macrocyclic ligand in relatively poor yield. A further variation on this reaction type allows the use of an enol ether (vinylogous ester), which provides more flexibility with respect to substituents (equation 17).104 The approach illustrated in equation (15), and Scheme 11 can be extended to include reactions of (3-diketones. The benzodiazepines, which result from reaction between 1,2-diaminobenzenes and (3-diketones, can also serve as precursors in the metal template reaction (Scheme 12).101 105 106 The macrocyclic complex product (46) in this sequence, being unsubstituted on the meso carbon atom, has been shown to undergo an electrochemical oxidative dimerization (equation 18).107... 

Three new macrocyclic ligands (187) when complexed with zinc(II) could promote ester hydrolysis and a kinetic study of the hydrolysis of 4-nitrophenyl acetate in Tris buffer at pH 8.63 in 10% (v/v) MeCN was earned out with these.153 The hydrolysis of lipophilic esters is also catalysed by zinc(H) in a complex of a long alkyl-pendant macrocyclic tetraamine (188) in micellar solution.154 A study with a copper chloride-containing micelle has compared its effectiveness in the hydrolysis of esters and amides.155... 

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