Aggregation metals/metal complexes

The utility of two photoreactive ID hydrogen-bonded aggregates of metal complexes in the formation of 1D CPs are described here. " ... 

It is often difficult to represent inorganic compounds with the usual structure models because these structures are based on complex crystals space groups), aggregates, or metal lattices. Therefore, these compounds are represented by individual polyhedral coordination of the ligands such as the octahedron or tetrahedron Figure 2-124d). 

A variety of materials has been proposed to modify the properties of asphaltic binders to enhance the properties of the mix (112), including fillers and fibers to reinforce the asphalt—aggregate mixture (114), sulfur to strengthen or harden the binder (115,116), polymers (98,117—121), mbber (122), epoxy—resin composites (123), antistripping agents (124), metal complexes (125,126), and lime (127,128). AH of these additives serve to improve the properties of the binder and, ultimately, the properties of the asphalt—aggregate mix. 

There are only a few weU-documented examples of catalysis by metal clusters, and not many are to be expected as most metal clusters are fragile and fragment to give metal complexes or aggregate to give metal under reaction conditions (39). However, the metal carbonyl clusters are conceptually important because they form a bridge between catalysts commonly used in solution, ie, transition-metal complexes with single metal atoms, and catalysts commonly used on surfaces, ie, small metal particles or clusters. 

The first one is the direct synthesis of metallic nanoclusters, not via formation of (hydro)oxides and their reduction in gas-phase, because the successive reduction for formed (hydro)oxides sometimes results in the size growth of metal particles due to the aggregation and/or sintering. The second one is the use of precisely designed metal complexes, which are well adsorbed on the support surfaces, as shown in Figure 1. 

In metal complexes of FTF5 and DPA, both single two-electron and double one-electron redox couples were observed. [(FTF5)Zn2] is diamagnetic, whereas the EPR spectmm of [(DPA)Zn2] was interpreted as that of a triplet that was complicated by aggregation. Why the ground electronic state of [(DPA)Zn2] is a triplet remains to be established a triplet porphyrin diradical was thought to be unique in porphyrin chemistry [LeMest et al., 1992]. 

Complexation of gold ions, [Au(I)], with peripheral phosphine groups of a P-based dendrimer was reported by Majoral et al. [185]. Transmission electron microscopy (TEM) was used to analyze the large aggregates formed by the dendritic gold complexes and a direct correlation was observed between the size of the particles and the dendrimer generation number. In a recent report [186], Majoral et al. further demonstrated that up to 48 diphosphino groups could be anchored to the surface of dendrimers and various dendritic metal-complexes... 

Our approach, to achieve a high dispersion of the metal compound while the oxide network is formed, is to employ metal complexes of the type LnM[X(CH2)3Si(OR)3]y in the sol-gel process [2]. The metal ions then cannot aggregate because of complexation, and the metal complexes cannot leach because they are linked to the oxidic support. These complexes are formed in situ on reaction of silanes of the type X(CH2)nSi(OR)3 with suitable metal salts. 

When supported complexes are the catalysts, two types of ionic solid were used zeolites and clays. The structures of these solids (microporous and lamellar respectively) help to improve the stability of the complex catalyst under the reaction conditions by preventing the catalytic species from undergoing dimerization or aggregation, both phenomena which are known to be deactivating. In some cases, the pore walls can tune the selectivity of the reaction by steric effects. The strong similarities of zeolites with the protein portion of natural enzymes was emphasized by Herron.20 The protein protects the active site from side reactions, sieves the substrate molecules, and provides a stereochemically demanding void. Metal complexes have been encapsulated in zeolites, successfully mimicking metalloenzymes for oxidation reactions. Two methods of synthesis of such encapsulated/intercalated complexes have been tested, as follows. 

Calculations of alkali metal allyl derivatives involving all alkali metals (Li-Cs) indicate a preferred geometry with the metal symmetrically bound in a predominantly electrostatic manner to all three carbon atoms.143 Solution studies of allyllithium in ether indicate the compounds to be highly aggregated in THF complex dynamic behavior is observed. 

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