Synthetic metal cations

The first synthetic organic pigments were used to shade or tone the weaker colorants and became known as toners. Metal toners usually contain one sulfonic acid group and often a carboxyUc acid group. The pigment is rendered iasoluble, ie, laked Ai a heavy metal cation. An example of a calcium salt is Lithol Rubine BK [5858-81-1] Vhl) (Cl Pigment Red 57 Cl 15850). 

The best characterized of these reactions involve the mercuric ion, Hg ", as the cation. The same process occurs for other transition-metal cations, especially Pd, but the products often go on to react fiirther. Synthetically important reactions involving Pd will be discussed in Section 8.2 of Part B. The mercuration products are stable, and this allows a relatively uncomplicated study of the addition reaction itself The usual nucleophile is the solvent, either water or an alcohol. The tenn oxymercuration is used to refer to reactions in... 

Cerrada, E., Laguna, M., Bartolome, J., Campo, J., Orera, V. and Jones, P.G. (1998) Cation-radical salts with organometallic gold anions. X-ray structure of TTFPh]2[Au(C6F5)2]. Synthetic Metals, 92(3), 245—251. 

M. Treeby, H. Mar.schner, and V. Roniheld, Mobilization of iron and other micronu-trient cations from a calcareous soil by plant-borne, microbial, and synthetic metal chelators. Plant Soil 114 211 (1989). 

The addition reactions discussed in Sections 4.1.1 and 4.1.2 are initiated by the interaction of a proton with the alkene. Electron density is drawn toward the proton and this causes nucleophilic attack on the double bond. The role of the electrophile can also be played by metal cations, and the mercuric ion is the electrophile in several synthetically valuable procedures.13 The most commonly used reagent is mercuric acetate, but the trifluoroacetate, trifluoromethanesulfonate, or nitrate salts are more reactive and preferable in some applications. A general mechanism depicts a mercurinium ion as an intermediate.14 Such species can be detected by physical measurements when alkenes react with mercuric ions in nonnucleophilic solvents.15 The cation may be predominantly bridged or open, depending on the structure of the particular alkene. The addition is completed by attack of a nucleophile at the more-substituted carbon. The nucleophilic capture is usually the rate- and product-controlling step.13,16... 

Kispert, L. D., J. Joseph et al. (1987). EPR study of arene radical cation salt crystals. Synthetic Metals 20 67-72. 

As mentioned in the Introduction, one of the synthetic approaches to stable nucleophilic carbenes involves C-deprotonation of imidazol-ium and related cations with alkali metal salts of strong bases such as NaH and KO Bu. Accordingly, the interactions with alkali metal cations with stable nucleophilic carbenes could prove to be important for understanding the solution behavior of the latter. Until recently, however, there were no examples of complexes of stable carbenes with... 

The broader subject of the interaction of stable carbenes with main-group compounds has recently been reviewed. Accordingly, the following discussion focuses on metallic elements of the s and p blocks. Dimeric NHC-alkali adducts have been characterized for lithium, sodium, and potassium. For imidazolin-2-ylidenes, alkoxy-bridged lithium dimer 20 and a lithium-cyclopentadienyl derivative 21 have been reported. For tetrahydropyrimid-2-ylidenes, amido-bridged dimers 22 have been characterized for lithium, sodium, and potassium. Since one of the synthetic approaches to stable NHCs involves the deprotonation of imidazolium cations with alkali metal bases, the interactions of alkali metal cations with NHCs are considered to be important for understanding the solution behavior of NHCs. 

IV. Complexes of Alkali and Alkaline-Earth Metal Cations with Synthetic Organic Ligands... 

Fig. 3.7 Top Relationship between the unit cell edge length a of synthetic goethites and various structurally incorporated metals. Bottom Rate of change of a per mol of substituted metal (= slope of the upper curves) vs. ionic radius of the respective metal cations (Gerth, 1990, with permission).

Selective alkylation of 6-keto esters via either anions or dianions is an important synthetic transformation. Equally, thioesters may be trans-esterified in the presence of thiophilic metal cations. These two features... 

Many borates are known that contain non-metal cations. Examples include the ammonium borates [39], such as the commercial products ammonium pentaborate, NH4[B506(0H)4] 2 H2O, and ammonium tetraborate, (NH4)2 [6405(011)4] 2 H2O, both of which contain isolated borate anions shown above (Figs. 5a and 6a, respectively) [40]. Isolated borate anions containing more than six boron atoms are rare. However, the mineral ammonioborite [(NH4)3[Bi502o(OH)g] 4 H20 = (NH4)20 5 B2O3 2 2/3 H2O), which may be prepared synthetically by prolonged reflux of a saturated solution of ammonium pentaborate, contains the unusual isolated anion [Bi502o(OH)g] , shown in Fig. 10 [41]. This anion is not known to occur in any metal borate, its formation is apparently directed exclusively by the ammonium cations which can donate H-bonds to interstitial water and the borate structural unit. 

According to this method, Fyles analyzed the transport rate of alkali metal cations for a series of 21 synthetic transporters (Figure 14). The whole molecules were designed to elucidate the structure-function relationship. They are composed of three parts core, wall, and head units. The core units were derived from tartaric acids so that the wall units may be fixed to provide structural control by incorporating both the polar and nonpolar functionality (Y and Z in Figure 14). The head groups (X) are attached to provide an overall amphiphilic nature. 

The hydrothermal method has been employed in recent years to synthesize a variety of solids that include aluminium phosphates (ALPOs) and other microporous transition-metal phosphates and transition-metal polychalcogenides (Davis Lobo, 1992 Haushalter Mundi, 1992 Liao Kanatzidis, 1990, 1992). Unlike zeolites, synthesis of ALPOs requires acidic or mildly basic conditions and no alkali metal cations. A typical synthetic mixture for making ALPO consists of alumina, H3PO4, water and an organic material such as a quaternary ammonium salt or an amine. The hydrothermal reaction occurs around 373-573 K. The use of fluoride ions, instead of hydroxide ions as mineralizer, allows synthesis of novel microporous materials under acidic conditions (Estermann et al, 1991 Ferey et ai, 1994). 

Crown ethers are synthetic compounds that envelop metal ions (especially alkali metal cations) in a pocket of oxygen ligands. Crown ethers are used as phase transfer catalysts because they... 

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