Complex systems, binuclear transition

Equally strong interactions do not necessarily have to exist in square planar binuclear complexes, a problem that is of great concern to us. There is very little information in the literature about the synthesis or properties of such materials. Possibly planar binuclear systems are the ethanetetraaldehyde-bridged nickel aminotroponeiminato complexes, 2, reported by Trofimenko (26). The preparation of the bisimidazole complexes 3 was described (27) of which the tetracarbonyl derivatives might well be the very first example of completely planar binuclear transition metal compounds that are capable of extended interactions. 

Some representative co-facial systems. The series (138)—(140) of mixed thiaaza donor ligands have been synthesized and all three have been shown to form binuclear complexes with transition metal ions (Lehn, 1980). In these, each metal ion is associated with one cyclic subunit as shown in (141) for (138). Complexes containing two Cu(n) ions or two Cu(i) ions have been obtained with each of (138)-(140) while (139), the... 

The transitions of type (c) are defined by two transition temperatures, one for decreasing (Ti/2j), and one for increasing temperature (Ti/2 ). Two-step transitions (Fig. Id), first reported in 1981 for an iron(III) complex of 2-bromo-salicylaldehyde-thiosemicarbazone [21], are relatively rare and have their origins in several sources. The most obvious is the presence of two lattice sites for the complex molecules. There are several examples of this [22]. In addition, binuclear systems can give rise to this effect, even when the environment of each metal atom is the same—in this instance the... 

In addition to the systems just mentioned, recent kinetic and mechanistic studies have included those involving copper(II) (409,410) and zinc(II) (411) species, various binuclear metal(II) complexes of first row transition elements (412-414), especially iron (407), cobalt (415), copper (305,416), and zinc (417,418), yttrium (419,420) and lanthanide (421,422) species, and thorium(IV) (423). 

A suitable model for the oxygen carrier protein hemerythrin is [Fe2(Et-HPTB)(OBz)](BF4)2 (Et-HPTB = AWAT,iV -tetrakis[(N-ethyl-2-benzimidazolyl)methyl]-2-hydroxy-l,3-diaminopropane, OBz = benzoate). It can mimic the formation of a binuclear peroxo iron complex in the natural system (101). The measured value of -12.8 cm3 mol1 for the activation volume of the oxidation reaction together with the negative value of the activation entropy confirm the highly structured nature of the transition state. 

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