Cadmium complexes macrocyclic

This area of macrocyclic coordination chemistry is also the subject of much recent activity, partly because the zinc and cadmium complexes have interesting spectroscopic and photochemical properties. 

Cadmium complexes of macrocyclic ligands have not been as widely studied as the corresponding zinc complexes, but the fact that cadmium macrocycles undergo easy metal exchange should make them attractive subjects for future study. The crystal structure of [Cd(TPP)(dioxane)j and its 113CdNMR characteristics have been reported.1144 The formation... 

As alluded to above, metal complexes of a number of lanthanide and actinide texaphyrin complexes have also been prepared. In the case of Dy(III) texaphyrin 9.74, as in the case of the bis-pyridine cadmium complex 9.61b, the metal center sits directly within the mean plane of the macrocycle (Figure 9.1.12). This result stands in direct contrast to the highly labile, typically sandwich-type 2 1 or 3 2 complexes observed for porphyrin complexes with these larger metal cations. ... 

A review of expanded porphyrin ligands can be found. The texaphyrins (8) can be considered as 22- 7r-electron benzannulene systems with an IS-tt-electron delocalization path, based on crystal structure data as well as NMR. The cadmium complex of the macrocycle is found to be planar with pentadentate coordination of the macrocycle to cadmium, which becomes seven-coordinate as a result of axial coordination to two pyridine molecules. The cavity is neariy circular with a center-to-nitrogen distance of 2.39 A. Because of the larger size of this macrocycle, metal ion coordination is generally seen with the larger transition metals and lanthanides. 

Tetraaza macrocycles nickel complexes, S Tetragonality copper(II) complexes, 603 Theophylline cadmium complexes, 957 Thermolysin zinc, 1006 Thiabendazole metal complexes, 951 Tollen s reagent, 780 Transcription DNA polymerases, 1007 Trans effect... 

Complexation and determination of formation constants has been studied with the tetramethyl-cyclam (l,4,8,ll-tetramethyl-l,4,8,ll-tetraazacyclotetradecane) ligand.686 A series of zinc N4 donor macrocyclic complexes with different ring sizes were synthesized and characterized for comparison with cadmium derivatives.687... 

In a similar manner, the potentially sexadentate macrocycle (21) yields Pb(n) and Cd(n) complexes which have unusual geometries (Drew etal., 1979). With Pb(n), the stereochemistry is hexagonal pyramidal with one axial site occupied by a water molecule and the other filled by a sterically-active lone pair of electrons on the metal ion. The Cd(n) complex is eight-coordinate (with a water molecule and a perchlorate group occupying axial positions) however the cadmium ion is not held centrally in the macrocyclic hole but is displaced to one side, presumably reflecting the... 

Crown ethers [364] have proved to be an excellent choice as ionophores for the fabrication of ion sensors because of their ability to complex selectively a particular ion. The cadmium selective sensors have been fabricated from poly(vinyl chloride) (PVC) matrix membranes containing macrocyclic ionophores benzo-15-crown-5 [365], monoaza-18-crown-6 [366], dibenzo-24-crown-8 [367], dicyclohexano-18-crown-6 [368], 3,4 ll,12-dibenzo-l,6,... 

The addition of macrocycles on CdS synthesis in reverse micelles induces a strong change in absorption spectra. For a given water content, a red shift of absorption onset is observed in presence of macrocycles. This effect is more pronounced in presence of Kryptofix 222 and when the CdS nanocrystallite synthesis is realized in presence of an excess of sulfide S2 ions (x = ). This red shift is characteristic of an increase in the average nanocrystallite size. It can be noticed that absorption of CdS particles synthetized in reverse micelles in presence of an excess of cadmium Cd2+ ions (x = 2) is reduced in presence of macrocycles. This indicates a decrease in the yield of CdS particles and is attributed to complexation of functionalized... 

In his early work Pedersen investigated crown ether complexation by UV spectroscopy. He reported that complexation caused a shift in the absorption maximum of dibenzo[18]crown-6 of about 6 nm to a longer wavelength (B-78MI52101). The test was not totally reliable as cadmium caused no change in the spectrum yet gave a crystalline complex. In general, however, UV-visible spectroscopy is of limited use in the study of macrocyclic complexes. 

Polyaza-, polythia-ligands. Recognition of transition metal ions. Replacing the oxygen sites with nitrogen or sulphur yields macrocycles and cryptands that show marked preference for transition metal ions and may also allow highly selective complexation of toxic heavy metals such as cadmium, lead and mercury [2.41-2.44, A.14]. 

Both zinc and cadmium form numerous complexes with amine ligands, ranging from NH3 through diamines such as ethylene diamine and substituted propylene diamines,54 to a variety of macrocycles.55 56 Pyridines and pyrazoles are also good ligands.57,58 In the case of 1,3,5-triaminocyclo-hexane, a regular octahedral complex cation is formed, as shown in Fig. 15-4. With 3-Me-pyrazine, tetrahedral [Zn(C4N2H6)4]2+ is formed.59... 

In a manner similar to that used to prepare 112, the reaction of the diformyl-tripyrrane 114 with o-phenylenediamine was found by Sessler and coworkers to result in the synthesis of a pentaazamacrocycle 115 (Scheme 13) [59], An X-ray structure of a derivative of 115 is shown in Fig. 19. Unfortunately, no structurally characterized metal complexes of 115 have been reported to date. However, oxidation of 115 in the presence of cadmium(II) was found to give the aromatic pentaaza-macrocycle metal complex 116, which has been characterized by X-ray diffraction [60]. The properties and chemistry of these tripyrroledimethine-derived texaphyrins is reported in the next section. 

Using a different metal salt, Cd(NOj)2, instead of CdClj oxidation reaction results in a slightly higher yield of the cadmium texaphyrin complex [60, 65]. However, upon purification, the product is obtained as a mixture of crystalline and non-crystalline solids. A single crystal X-ray diffraction study of the crystalline portion of the sample gave an unexpected result. The structure obtained (Fig. 20) revealed a six-coordinate pentagonal pyramidal cadmium (II) complex 156 (c.f. Scheme 20) where one of the two possible axial ligation sites is occupied by a benzimidazole [65]. The five donor atoms of the pentadentate texaphyrin macrocycle complete the coordination sphere about the cadmium with the cadmium... 

Many dithiocarbamate complexes of zinc, silver, cadmium or mercury improve emulsion stability, including bis(dibenzyldithiocarbamato)-zinc(II) or -cadmium(II) and silver(I) diethyldi-thiocarbamate. Cadmium salts, mixed with citric acid or tartaric acid and added to the emulsion, are reported to be effective. Mercury(II) complexes of ethylenediaminetetraacetic acid (EDTA) and related ligands and of solubilized thiols such as (4) can be used. Other coordination compounds reported include EDTA and related ligand complexes of Co and Mn, mixtures of Co salts with penicillamine (5) and macrocyclic complexes of Ag such as (6). The latter compounds may be used in diffusion transfer systems in which transferred maximum densities are stabilized. 

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