Macrocycle metal containing

Although most of the macrocycles that contain phosphorus or arsenic which have thus far been prepared, are primarily transition metals binders, two compounds have been prepared which are essentially crown ethers containing phosphorus. Kudrya, Shtepanek and Kirsanovhave prepared two compounds which are essentially polyoxygen macrocycles but which contain one or two methylphosphonic acid esters as part of the ring. These two macrocycles are shown below as 7d and 17 and are both prepared by the reaction of 2,2 [oxybis(ethyleneoxy)] bisphenolate with methylphosphonic dichloride in a mixture of acetonitrile and benzene. The crystalline monomer 16) and dimer 17) were isolated in 17% and 11% yields respectively as indicated in Eq. (6.13). 

Perspectives for fabrication of improved oxygen electrodes at a low cost have been offered by non-noble, transition metal catalysts, although their intrinsic catalytic activity and stability are lower in comparison with those of Pt and Pt-alloys. The vast majority of these materials comprise (1) macrocyclic metal transition complexes of the N4-type having Fe or Co as the central metal ion, i.e., porphyrins, phthalocyanines, and tetraazaannulenes [6-8] (2) transition metal carbides, nitrides, and oxides (e.g., FeCjc, TaOjcNy, MnOx) and (3) transition metal chalcogenide cluster compounds based on Chevrel phases, and Ru-based cluster/amorphous systems that contain chalcogen elements, mostly selenium. 

The presence of the cyclic backbone in ligands of this type makes a substantial contribution to their metal-ion complexing ability even though coordination involves donors which are not directly incorporated in the ring fragment. The origins of the enhanced stability of the metal-containing species may be considered to reflect the operation of an indirect macrocyclic effect (see Chapter 6) in these systems. 

As the flexibility of the macrocycle increases, then mismatch hole-size effects are expected to be moderated. In any case, as discussed in Chapter 1, a metal ion which is too large for the cavity may be associated with folding of a flexible macrocycle thereby allowing normal metal-ligand bond distances to be achieved. However, this is not always the case, and a number of examples of unfolded macrocyclic complexes containing compressed metal-donor distances are known (Henrick, Tasker Lin-doy, 1985). 

Metalated container molecules can be viewed as a class of compounds that have one or more active metal coordination sites anchored within or next to a molecular cavity (Fig. 2). A range of host systems is capable of forming such structures. The majority of these compounds represent macrocyclic molecules and steri-cally demanding tripod ligands, as for instance calixarenes (42), cyclodextrins (43,44), and trispyrazolylborates (45-48), respectively. In the following, selected types of metalated container molecules and their properties are briefly discussed and where appropriate the foundation papers from relevant earlier work are included. Porphyrin-based hosts and coordination cages with encapsulated metal complexes have been reviewed previously (49-53) and, therefore, only the most recent examples will be described. Thereafter, our work in this field is reported. 

III. Metalated Container Molecules of Binucleating Polyaza-Dithiophenolate Macrocycles... 

An example of the above mentioned cascade complexation of carboxylates by macrocyclic receptors containing metal ionic centers is the inclusion of oxalate by the dien dicobalt complex 9 (Martell, Mitsokaitis) [12]. Similarly, the -cyclodextrin (jS-CD) 10, modified with a zinc cation bound by a triamine side chain, encapsulates anions like 1-adamantylcarboxylate in its cavity, fixing them by combined electrostatic and hydrophobic interactions [13], Zinc s group achieved the enantioselective transport of the potassium salts of N-protected amino acids and dipeptides by making use of the cation affinity of... 

Macrocyclic complexones contain more than one aminoacetic group, which is bound over the N atom to a cyclic unit as in the case of the tetraaza macrocycles (15). Different selection effects are found in the case of these ligands (see Chapters 21.1-21.3 of this volume).67 The pAT values of the acids are much higher than those of edta they almost explain the high values of the stability constants with alkaline earth and transition metal cations. The differences in log K, between Ca2+ and Mg2+ are very high and similar to those observed for egta. For the transition metals the cyclic complexones have no advantage over the non-cyclic ones such as edta and cdta. 

Propano-linked macrocyclic complexes (69) have been shown to undergo oxidative dehydrogenation with ease under mild conditions (equation 27).157>162 This reaction occurs for nickel(II), copper(II) and cobalt(II) complexes and leads to cobalt(III) dibenzocorromins , which are simple models of the vitamin B12 coenzyme nucleus.163 Macrocyclic complexes containing this ligand chromophore had already been prepared by a direct metal template method (Scheme 29).164 165 However, the oxidative dehydrogenation route offers greater experimental certainty and variety. 

Plieger, P. G., Tasker, P. A., Galbraith, S. G., Zwitterionic macrocyclic metal sulfate extractants containing 3-dialkylami-nomethylsalicylaldimine units. Dalton Trans. 2004, 313-318. 

The template syntheses of macrocyclic ligands, containing N,P-, P,P-, S,S-, and 0,E-atoms (E = S, Se, Te) [318,358] as donor centers have been reported. The possibility of formation of binuclear structures on a metal matrix using fragments of crown-ethers is shown [318]. However, a detailed examination of these syntheses is beyond the limits of the present monograph. 

Besides the ferrocene crown ether ligands described earlier, a variety of related macrocyclic ferrocenophanes containing various sulfur, oxygen, and nitrogen heteroatoms have been reported by a number of groups (110-115) (Scheme 21). These ligands complex transition metal guest cations such as Ag(I), Cu(I), and Pd(II) (116,117). Of particular... 

D nanoribbons and nanowires of different metal-containing Pcs have also been prepared by organic vapor-phase deposition (OVPD), a technique used to fabricate organic millimeter-sized crystals, thin films, or nanostructures [211], Scanning electron microscopy (SEM), TEM, x-ray diffraction (XRD), and absorption measurement studies have revealed that the morphology of the nanostructures was strongly dependent on the chemical nature of the deposited macrocycle, the nature and the temperature of the substrate, and the source-to-substrate distance. 

Although macrocyclic receptors containing N and O donor atoms are suitable for detection of alkali metal cations, the detection of alkali earth cations required application of chelating receptors based on amino acids with EDTA-like spatial arrangement, eg bis(o-amino-phenoxy)-ethane-A, N, N, A -tetraacetic acid (BAPTA) [9,12], The most common calcium PET sensors are shown in Figure 16.6. 

One of the first metal-containing NO fluorescent sensors contains an Fe(II) macrocyclic complex connected with quinoline ligand on a pendant arm (Figure... 

The preferential coordination geometry of the template metal ion determines the nature of the macrocycle that is formed, e.g., Ni2 + and Cu2+ are particularly effective template ions for the synthesis of N-donor macrocycles containing 4 nitrogen atoms that can be arranged in a plane and, hence, form a square planar macrocycle-metal complex. 

The ratio of the size of the metal ion and the radius of the internal cavity of the macrocyclic polyether determines the stoichiometry of these complexes. The stoichiometry of these complexes also depends on the coordinating ability of the anion associated with the lanthanide. For example, 12-crown-4 ether forms a bis complex with lanthanide perchlorate in acetonitrile while a 1 1 complex is formed when lanthanide nitrate is used in the synthesis [66]. Unusual stoichiometries of M L are observed when L = 12 crown-4 ether and M is lanthanide trifluoroacetate [67]. In the case of 18-crown-6 ligand and neodymium nitrate a 4 3 stoichiometry has been observed for M L. The composition of the complex [68] has been found to be two units of [Nd(18-crown-6)(N03)]2+ and [Nd(NCh)<--)]3. A similar situation is encountered [69] when L = 2.2.2 cryptand and one has [Eu(N03)5-H20]2- anions and [Eu(2.2.2)N03]+ cations. It is important to note that traces of moisture can lead to polynuclear macrocyclic complexes containing hydroxy lanthanide ions. Thus it is imperative that the synthesis of macrocyclic complexes be performed under anhydrous conditions. 

Nearly all iron complexes of synthetic macrocyclic ligands contain nitrogen either as the only ligand atom or as the major donor present. Moreover, most macrocyclic ligands are tetradentate usually presenting a roughly planar N4 donor set to the centrally complexed metal ion. The comprehensive review by Melson390 of the coordination chemistry of macrocyclic compounds should be consulted for work published up until 1978. 

These ligands are especially important because many naturally occurring, metal-containing compounds such as chlorophylls, heme, cytochromes, etc., contain macrocycles. Some examples of these ligands are shown in Fig. 9-3. 

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