Metal poly complexe

Metal-acetylide complexes have been used as a unit of organometallic polymers that have metallic species in the main chain [20]. Representative examples are metal-poly(yne) polymers (19) of group 10 metals depicted in Scheme 5. These polymers are easily prepared from M(PR3)2Cl2 (M=Pt, Pd) and dialkynyl compounds catalyzed by Cu(I) salts in amine. Recently, this synthetic method was successfully applied to the construction of metal-acetylide dendrimers. 

Metal-acetylide complexes including metal-poly(yne) polymers often show unique properties [21-23]. Thus, metal-acetylide dendrimers are of interest because amplification of the functionality due to metal-acetylide units based on three-dimensional assembly with a regular dendritic structure is expected. 

Hydrolysis increases the terpolymer limiting viscosity number in water by a factor of up to 45. Other previously published data(66-68) show that these terpolymers are nonnewtonian viscosifiers, metal-ion complexing agents, and effective flocculators. These materials are still "small" molecules in aqueous solution, however, and do not function as effectively when used 1. as nonnewtonian viscosifiers or 2. drag reducing agents as do poly(l-amidoethylene-co-(sodium 1-carboxylatoethylene)) copolymers. 

The most well-developed recent examples of catalysis concern catalysts for oxidation reactions these are essentially achiral or chiral metal-salen complexes. Taking into account a number of results suggesting the importance of a degree of mobility of the bound complex, Sherrington et al. synthesized a series of polymer-supported complexes in which [Mn(salen)Cl] units are immobilized in a pendant fashion by only one of the aromatic rings, to polystyrene or poly(methacrylate) resin beads of various morphology (Figure 6).78,79... 

Adams, R.D., Cotton, F.A. (Eds.), Catalysis by Di- and Poly-nuclear Metal Cluster Complexes. Wiley-VCH New York, 1998. 

A first generation poly(amido amine) dendrimer has been functionalized with three calyx[4]arenes, each carrying a pyrene fluorophore (4) [30]. In acetonitrile solution the emission spectrum shows both the monomer and the excimer emission band, typical of the pyrene chromophore. Upon addition of Al3+ as perchlorate salt, a decrease in the excimer emission and a consequent revival of the monomer emission is observed. This can be interpreted as a change in the dendrimer structure and flexibility upon metal ion complexation that inhibits close proximity of pyrenyl units, thus decreasing the excimer formation probability. 1H NMR studies of dendrimer 4 revealed marked differences upon Al3+ addition only in the chemical shifts of the CH2 protons linked to the central amine group, demonstrating that the metal ion is coordinated by the dendrimer core. MALDI-TOF experiments gave evidence of a 1 1 complex. Similar results have been obtained for In3+, while other cations such as Ag+, Cd2+, and Zn2+ do not affect the luminescence properties of... 

Photolysis of Transition-Metal Poly hydride Complexes 363... 

Abstract In this chapter, the depression mechanism of five kinds of depressants is introduced respectively. The principle of depression by hydroxyl ion and hydrosulphide is explained which regulates the pH to make the given mineral float or not. And so the critical pH for certain minerals is determined. Thereafter, the depression by cyanide and hydrogen peroxide is narrated respectively which are that for cyanide the formation of metal cyanide complex results in depression of minerals while for hydrogen peroxide the decomposition of xanthate salts gives rise to the inhibitation of flotation. Lastly, the depression by the thio-organic such as polyhydroxyl and poly carboxylic xanthate is accounted for in detail including die flotation behavior, effect of pulp potential, adsorption mechanism and structure-property relation. 

IV. Metal Cluster Complexes Derived from 1,3-Diynes or Poly-ynes. 130... 

METAL CLUSTER COMPLEXES DERIVED FROM 1,3-DIYNES OR POLY-YNES... 

Many examples of metal cluster complexes featuring diyne or higher poly-yne ligands are known, and have generally been obtained by three main routes. 

Lithium polymer batteries are similar in principle to the lithium batteries described above but the electrolyte is a polymer. The advantage of these batteries is the absence of liquid in the cell and so the batteries do not leak. The polymer electrolyte is a polymer-alkali metal salt complex. The best known such electrolytes are complexes of poly (ethylene) oxide (PEO). 

The oxidations by [Ni,ll([9]aneN3)2]3+ and [Nim([10]aneN3)2]3+, of a series of metal poly(pyridine) complexes, have been investigated (107, 146, 149). A typical reaction of this type is seen in Eq. (9), where... 

Like many late transition metals, nickel has featured, albeit briefly, in the pursuit of poly(pyrazolyl)borate-metal-carbollide complexes. Thus, [c/oso-3-(r 2-Ph2Bp)-3,l,2-NiC2B9H11] (90 ) has been obtained as the tet-ramethylammonium salt,39 via the reaction of [Me4N][Ph2Bp] with the neutral bisphosphine nickel dicarbollide [doso-3,3-(PhEt2P)2-3,l,2-... 

Aromatic primary diamines, dithiols, and diethynyl compounds are oxidatively polymerized with metal-amine complexes as the catalyst to yield poly (azopheny-lene) [78], poly(disulfide) [79], and polydiyne [80], respectively (Figure 7, Eq. 

Figure 4.15 Schematic representation of the sequential steps taken for the formation of multilayers based on electrostatic self-assembly using cationic polymers and anionic a-ZrP sheets (see text for further details). Reprinted from Coord. Chem. Rev., 185-186, D.M. Kaschak, S.A. Johnson, C.C. Waraksa,J. Pogue and T.E. Mallouk, Artificial photosynthesis in lamellar assemblies of metal poly(pyridyl) complexes and metalloporphyrins, 403-416, Copyright (1999), with permission from Elsevier Science...

Table 3. Spectral data of metal-poly-yne polymers and monomer complexes Polymers" IRb UVC P-NMR"...

Considerations based on the Stuart model of Pt-D1 polymer (Fig. 4) along with structure40) of the model complex imply that the high solubility of the metal-poly-yne polymers may be attributed to bulky substituents on phosphorus which efficiently cover the polymer backbone and decrease intermolecular interactions between polymer molecules. This is supported by the fact that 1) the solubility of the polymers decreases in the order... 

The general patterns of structures and bonding in metal poly-olefin complexes are similar to those in olefin complexes. Linear, branched and cyclic polyolefin complexes are known. The bonding is delocalized over the carbon atoms and the metal(s). These species also play important roles in organic syntheses. 

Shima, T. and Hou, Z.M. (2006) Hydrogenation of carbon monoxide by tetranuclear rare earth metal poly-hydrido complexes. Selective formation of ethylene and isolation of well-defined polyoxo rare earth metal clusters. Journal of the American Chemical Society, 128, 8124. 

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