Copper cobalt dimer

The first mechanism is. in fact, reminiscent of the well-known copper-catalyzed dimerization of acetylene viny(acetylene being the main by-product of this process. This side reaction can, however, be inhibited to some extent by the use of cobalt salts as additives [IS]. The cyanation of acetylene and of alkenyl halides is also promoted by Co and Ni cyanides and Pd catalysis. A reducing reagent, such as Zn or NaBll4, has been used in conjunction with cobalt cyanide complexes, and the formation of. succinonitrile has been reported to result from the basebase-catalyzed hydrocyanation of acrylonitrile. 

Analogously, pyrazolyl-aluminate and -indate ligands have been prepared <75JCS(D)749) and their chelating properties evaluated with cobalt, nickel, copper and zinc. Gallyl derivatives of pyrazoles and indazoles have been extensively studied by Storr and Trotter e.g. 75CJC2944) who determined several X-ray structures of these compounds. These derivatives exist in the solid state as dimers, such as (212) and (288). A NMR study in acetone solution showed the existence of a slow equilibrium between the dimer (212) and two identical tautomers (289) and (290) (Section 4.04.1.5.1) (81JOM(215)157). 

Related compounds with other transition metals have been studied only sparsely, e.g., with nickel(II) [198], cobalt(III) [174], and rhodium(lll) [199, 200]. A series of dimeric copper(ll) complexes [[Cu(L BF2)S][X] is also known and exhibits interesting magnetic effects associated with electron spin exchange between the copper(ll) ions [201]. 

The importance of metal coordination compounds in biological systems has led to the study of polydentate Schilf base complexes of cobalt(II), nickel(II), and copper(II) (204, 205). Dimers have been observed in the spectra of complexes of both tri- and tetradentate ligands [e.g., salicylaldehydeand A,A-bis(salicylidene)ethylenediamine]. The parent ions form the base peaks, and the spectra are characterized... 

The compounds discussed in this section are restricted to nickel, as the existence of palladium (I) or platinum (I) compounds has not been established. Since nickel(I) contains nine d-electrons, analogies with copper(II) might be expected, but these do not arise there are, however, certain similarities with cobalt(O), particularly in the tendency to dimerization. 

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... 

Complexes of 107 have been isolated for copper(II), cobalt(II), and nickel(II) cations103). Condensation of 2,6-diaminopyridine with 108 affords the dimeric macrocycle 111 (70%). No complexes have been reported for ligands 111l08) or 113104 106>. in addition, the reaction of l,3-6is[(l-imino-4,5,6,7-tetrahydro-3-iso-indoline)amino]benzene with 2,6-diaminopyridine gives 113 (70%) 104>107>. 

The formation of a dimerized extracted species was first reported for the extraction of copper(II) with propanoic acid (40, 41). Later, nickel and cobalt were found to be extracted as dimers (22), and a mixed copper(II) carboxylate dimer involving acetate and decanoate was reported (147). More recently, attention has been drawn to the extraction of heteropolynuclear metal carboxylates (90, 91). 

In a related investigation to that just discussed, the tetramethyl-substituted quaterpyridine 37, which was designed to promote co-ordination in a twisted configuration, yielded complexes with 1 1 and 2 1 (metal ligand) stoichiometries with manganese(II) and cobalt(II). With copper(I), a dimeric helical complex of... 

Both in the solid state and in non-donor solvents the cobalt complexes of the Schiff bases X-saldpm (26) have the formula, Co(X-Saldpm)2 and are tetrahedral whereas the nickel(ii) and copper(ii) analogues are square-planar, irrespective of X. The crystal structure of NN -ethylenebis(thiosalicylideneiminato)cobalt(ii) shows centro-symmetric dimers. ° The crystal structure of l,6-bis-(2-hydroxyphenyl)-2,5-diaza-... 

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