Metal cation templates

In this system, however, intermolecular dimerization may take place competitively with intramolecular dimerization. To rule out this possibility, compound 5, in which two anthracenes are linked by two polyether chains, was synthesized.171 It was found that intramolecular photodimerization proceeds rapidly in the presence of Na+ as the template metal cation. Compound 6 was also synthesized.181 Although this compound has not been applied in a photoswitch system, it displays a remarkable fluorescence change upon binding with RbC104 or H3N+(CH2)7NHj.[81 Yama-shita et al.[9] also synthesized 7, in which intermolecular photodimerization of anthracene is completely suppressed. The photochemically produced cyclic form 8 displayed excellent Na+ selectivity. 

Fig. 4 The apparent pseudo-first-order rate constant /cobs (s ) for the formation of benzo-18-crown-6 as a function of the concentration of templating metal cation (M + = Li +, Na+, K +, Rb +, and Cs + ).53...

Transesterification in the presence of a templating metal cation has been used to prepare some tetra-ester polyether macrocycles from dimethyl malonate [equation (16)], and intramolecular transesterification of (75) is one of the... 

One of the prime tenets of the template effect is that a cation of appropriate size coordinates with the heteroatom binding sites in the incipient ring system. Evidence to be discussed below indicates that there is a clear relationship between the size of the coordinating cation and the size of the ring formed. Before presenting this evidence, it is useful to note the approximate ring sizes of common crowns and the known ionic diameters of sundry metal cations. This is done in Table 2.1. 

The one-pot synthesis of 9 described above appears to afford only modest yields of azacrowns. One might wonder why any crown at all would be formed under non-high dilution conditions intended to yield only open-chained material. Vogtle suggests that this can be explained in terms of template, steric and entropy effects . These factors are of doubtless significance, but it is interesting to note that in the synthesis of poly-azamacrocycles, Richman and Atkins found that there was no significant template effect observed. The question of the template effect in Ihe syntheses of 9 has recently been addressed by Kulstad and Malmsten They conclude that the formation of 9 is assisted by the presence of alkali metal cations. 

Shinkai [15] concluded that p-zert-butyl calix[n]ar-ene tetra esters form stable monolayers at the air-water interface and the metal responds, therein, quite differently from that in solution. They reported that examination of the metal template effect on the conformer distribution established that when the metal cation present in the base used serves as a template, the cone conformer results are predominant [16]. Hence, Na in... 

Chiral-at-metal cations can themselves serve as chirality inducers. For example, optically pure Ru[(bipy)3] proved to be an excellent chiral auxihary for the stereoselective preparation of optically active 3D anionic networks [M(II)Cr(III)(oxalate)3]- n (with M = Mn, Ni), which display interesting magnetic properties. In these networks all of the metalhc centers have the same configuration, z or yl, as the template cation, as shown by CD spectroscopy and X-ray crystallography [43]. 

In the reaction of unprotected uridine with tri(imidazolyl-l)phosphine (ratio 1 1.5) under mild conditions (THF, — 78° to 0 °C, 10 min) and subsequent oxidation with iodide, two types of polymers [(Up)n (n = 2-6) and (Up)nU (n = 2—5)] are formed. Additives such as metal cations or polynucleotides (poly U and poly A) acting as templates in the oxidation process showed a significant effect on the ratio of the 3, 5 -linked to 2, 5 -linked oligomer 17 177 ... 

Aza macrocycles have also been used as templating agents in the formation of zinc and other metal cation-containing aluminophosphates via hydrothermal synthesis.705 The zeolite-like structures have been formed in the presence of cyclam- and hexaaza-based macrocycles. 

Polymeric pseudocrown ether networks have been generated in situ by the photopolymerization of poly(ethylene glycol) diacrylate transition metal complexes <00CM633>, and the effect of metal ion templation was evaluated. The 1,6,13,18-tetraoxa[6.6]paracyclophane-3,15-diyne (termed pyxophanes) was prepared from hydroquinone and l,4-dichlorobut-2-yne it forms size-selective 7i-complexes with alkali metal cations <00CC2377>. Dibenzo[ ]crown-m have been used in numerous elegant studies in which they were the needles that were threaded by diverse reagents the resultant... 

Since Pedersen s original work on the use of cations to template the formation of crown ethers [18-20], a large number of different templating agents for macro-cyclization reactions have been reported. While the initial work concentrated on the use of metal cations, further developments demonstrated that species with hydrogen bonding donor or acceptor properties could be equally useful to template the synthesis of macrocyclic molecules. 

The template synthesis method involves the diffusion of ligand precursors into the pores of a zeolite where they can assemble around an intrazeolite metal ion that acts as a template. This approach was first used in 1977 for the intrazeoHte synthesis of Cu, Co and Ni phthalocyanines by the condensation of four molecules of dicyanobenzene around the metal cation within the cages of NaY [132, 174]. 

Until now syntheses along path d) of Figure 3 are known only for small bicyclic systems, for instance N(CH2CH20)3B from triethanolamine and B(OH)3 (87), N(CH2CH2CH2)3B from triallylamine and BH3 (88). However, macrobicyclic structures may be obtained in this way from a tripod type structure by making use of the template effect of a complexed transition metal cation, which remains included in the product (89-91). 

Ions other than metal cations may also act as templating agents, for example in the synthesis of zeolites and mesoporous silicas by templating about alkali metal cations and large quaternary ammonium ions (Section 9.2.2). Similarly the synthesis of large polyoxovanadate cages is templated by the presence of ions such as Cl- or a combination of NH4+ and Cl-. 

Relatively simple reagents containing a salen -like metal binding unit with protonatable pendant tertiary amine groups to accommodate the sulfate dianion have been developed to establish proof-of-concept,[82] and the incorporation of the metal cation in the salen cavity has been shown to template the sulfate-binding site and enhance extraction (Figure 10). [83]... 

The scope of the tether-directed remote functionalization has been expanded from Cgo to the higher fullerene C70, and the described reactions are completely regioselective, featuring, in the case of C70, the kinetically disfavored addition pattern. The crown ether is a real template, since it can be readily removed by transesterification, giving a much-improved access to certain bis-adducts that are not accessible by the direct route. Cation-binding studies by CV reveal that cyclophane-type crown ethers derived from C60 and C70 form stable complexes with metal cations, and a perturbation of the fullerene reduction potentials occurs because the cation is tightly held close to the fullerene surface. This conclusion is of great importance for future developments of fullerene-based electrochemical ion sensors. 

---