Charged complexes

Complex Ion Formation. Phosphates form water-soluble complex ions with metallic cations, a phenomenon commonly called sequestration. In contrast to many complexing agents, polyphosphates are nonspecific and form soluble, charged complexes with virtually all metallic cations. Alkali metals are weakly complexed, but alkaline-earth and transition metals form more strongly associated complexes (eg, eq. 16). Quaternary ammonium ions are complexed Htde if at all because of their low charge density. The amount of metal ion that can be sequestered by polyphosphates generally increases... 

The possible mechanism of ionization, fragmentation of studied compound as well as their desoi ption by laser radiation is discussed. It is shown that the formation of analyte ions is a result of a multi stage complex process included surface activation by laser irradiation, the adsoi ption of neutral analyte and proton donor molecules, the chemical reaction on the surface with proton or electron transfer, production of charged complexes bonded with the surface and finally laser desoi ption of such preformed molecules. 

EXTRACTATION AND CONCENTRATION OF DIFFERENT-CHARGED COMPLEXES OF SOME PLATINUM METALS WITH... 

Method of Rh(III) - Ru(III) separation and isolation them from rai e and nonferrous metals based on formation of different charged complexes with varied stability has been proposed. Possibility of sepai ation of Ru(III), Rh(III), Pd(II), Pt(II) by water-soluble extractants from concentrated thiocyanate solutions has been displayed. Accelerated procedures of extraction-photometric determination of Rh(III), Ru(III) in solutions and waste products, which ai e chai acterized by high selectivity, availability, usage of non-toxic extractants have been worked out. 

BrMn(CO)5] reacts with pyrazolate ion to yield the charged complex 38 (69JA5410). Here the metals are bridged by three pyrazolate ligands (71IC1372). 

In the 3 + - and 1+-charged complexes there is a central Au atom and eight peripheral Au atoms, all coordinated to phosphine ligands, but there are differences in the geometry of the Au cores (respectively, XI, XII, and XIII). 

Interfacial formation of labile and charged complexes can facilitate a subsequent substitution reaction to produce an extractable complex. 

Scientists at Bristol-Myers Squibb used the a-ketoamide functionality to extend binding to the prime side [147]. The glycine carboxylic acid (Compound (5), Table 2.5) was identified as the most effective extension. Modelling studies, coupled with SAR, suggested that there is either hydrogen bonding or a charge complex of the acid with Lys-136 and Arg-109. 

Likewise, cationic acceptors afford mixed (positively) charged complexes with electron-rich donors,11 i.e., [D, A+] and anionic donors associate with electron-poor acceptors to form mixed (negatively) charged complexes,12 i.e., [D-, A]. In each case, the intermolecular (ionic) complexation or association represents the highly oriented organization of the donor/acceptor pair (independently of whether they bear positive, negative or no charge) that is often sufficient to afford crystalline complexes amenable to direct X-ray structure elucidation.13... 

The surface sites and complexes lie in a layer on the mineral surface which, because of the charged complexes, has a net electrical charge that can be either positive or negative. A second layer, the diffuse layer, separates the surface layer from the bulk fluid. The role of the diffuse layer is to achieve local charge balance with the surface hence, its net charge is opposite that of the sorbing surface. Double layer theory, applied to a mixed ionic solution, does not specify which ions make up the diffuse layer. 

Electrodes based on solutions of cyclic polyethers in hydrocarbons show a selective response to alkali metal cations. The cyclic structure and physical dimensions of these compounds enable them to surround and replace the hydration shell of the cations and carry them into the membrane phase. Conduction occurs by diffusion of these charged complexes, which constitute a space charge within the membrane. Electrodes with a high selectivity for potassium over sodium (> 1000 1) have been produced. 

Two examples of aquation/anation studies of chloro-platinum(II) complexes of possible medical relevance appeared in subsection 1 above 202,207). Aquation of cisplatin is slower in the presence of DNA but not in the presence of phosphate 220). DNA also inhibits substitution in [Pt(terpy)(py)]2+ and related complexes. For reaction of these charged complexes with iodide ion inhibition is attributable to electrostatic interactions - the complex is concentrated on the double helix and thus separated from the iodide, which distances itself from the helix. Intercalation of these complexes within the helix also serves to make nucleophilic approach by neutral reagents such as thiourea more difficult 221). 

Electrostatically-controlled pre-association interactions have an important effect on rates for [Pd(dien)Cl]+ reacting with thione-containing nucleosides, nucleotides and oligonucleotides, as is often the case for reactions between metal complexes and this type of biological ligand. Interaction between the charged complex and the polyanionic oligonucleotide surface leads to an increase in both enthalpy and entropy of activation in the DNA or model environment (252). 

A very different neutrally charged complex for alkane activation has been reported recently and is shown in Scheme 34(A). The compound is a hydridoplatinum(II) complex bearing an anionic ligand based on the familiar nacnac-type, but with a pendant olefin moiety (97).This complex is extremely soluble in arenes and alkanes and activates C-H bonds in both types of hydrocarbons. This is indicated by deuterium incorporation from deuterated hydrocarbon into the substituents on the arene of the ligand and into the Pt hydride position (A A-d27, Scheme 34). The open site needed for hydrocarbon coordination at Pt(II) is created by olefin insertion instead of anion or solvent substitution (97). 

Solvent effects A solvent may stabilize an intermediate, decreasing Ea and increasing the rate of the reaction. Charged-complexes are stabilized by polar solvents. 

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