Hydrated metal chlorides

Preparation of Complexes. Ln(ClOfj3 3 OMPA x H O. The hydrated metal chloride (0.0015 moles) was dissolved in 8 ml. of methanol. A stoichiometric amount of AgC104 H2O was added to precipitate AgCl. The filtrate was dehydrated with 2 ml. of 2,2-dimethoxypropane (J6) for 45 min., and 0.0077 moles of OMPA was added. Excess ether was added to precipitate the complex. The compounds were dried under vacuum at room temperature. The complexes where Ln is La, Ce, Sm, Eu, Dy were recrystallized from a methanol-ether solution. 

Crystals, mp 104. Vapor press at 20s 7.5 X 10 5 mm Hg, Very sol in most organic solvents and insol in water. Siable in presence of organic and inorganic alkalies stable to ihe action of hydrated metal chlorides. LDW orally in male female rats 39, 60 mg /kg, T. B- Gaines Toxicol Apph... 

CHEMICAL PROPERTIES stable in presence of organic and inorganic alkalies stable to the action of hydrated metal chlorides compatible with most fertilizers, herbicides, fungicides and insecticides incompatible or reacts strongly with concentrated mineral acids, active metals, acid catalysts, acid oxidizing agents, phenols FP (NA) LFLAJFL (NA). 

Several surface-mediated reactions leading to metal carbonyl clusters start from hydrated metal chlorides on wet silica it is also known that the presence of water can result in the formation of cluster anions at the expense of coordinated carbonylsJ l Hydridic cluster anions can be active in the water-gas shift reaction (WGSR), the Fischer-Tropsch and other reactions, as discussed belowJ ... 

We have, over the past few years, been developing a new series of homogeneous catalysts that do not contain such phosphine or phosphite ligands (and that are indeed deactivated by them), based on pentamethyl-cyclopentadienyl-rhodium and -iridium compounds. The parent complexes [M(C5Me5)Cl2]2 (1, M = Rh or Ir) are readily obtained from hexamethyl Dewar benzene and the appropriate hydrated metal chloride in a two-step reaction (2). 

Figure 14.1. A typical titration curve for hydrated metal chlorides in the gelation solvents (case shown CuCli 6 H2O 0.66 M in DMF).

Tetrakis(hexafluoroisopropoxides) of titanium, zirconium, and hafnium have been prepared by the reaction of sodium hexafluoroisopropoxide in an excess of hexafluoroisopropyl alcohol with the anhydrous metal chloride, and the spectroscopic properties are reported. The authors note that, in their experience, application to the Group IV transition metals of the previously published method for metal hexafluoroisopropoxide synthesis gives poor yields of material containing metal, fluorinated alkoxides, and co-ordinated ammonia. Dehydration of the hydrated metal chloride with methyl orthoformate and addition of hexafluoroisopropyl alcohol, followed by passage of dry ammonia through the solution, gives satisfactory yields for yttrium, lanthanum, neodymium, and erbium. 

Diethylamine, CH3CH2)2NH. B.p. 55-5°C. Forms a crystalline i hydrate. Prepared by the action of a boiling solution of sodium hydroxide on nitrosodielhylaniline. Forms crystalline compounds with many metallic chlorides. 

Precipitated (hydrated) siUca reacts vigorously with fluorosulfuric acid to give siUcon tetrafluoride [7783-61-1] (21), but glass (qv) is not attacked in the absence of moisture (20). Alkali and alkaline-earth metal chlorides are readily converted to fluorosulfates by treatment with fluorosulfuric acid (7,13,22,23). 

Nitro compounds can be further reduced to hydrazo compounds with zinc and sodium hydroxide, with hydrazine hydrate and Raney nickel,or with LiAlH4 mixed with a metal chloride such as TiCU or VCl3. The reduction has also been accomplished electrochemically. 

Certain other metal ions also exhibit catalysis in aqueous solution. Two important criteria are rate of ligand exchange and the acidity of the metal hydrate. Metal hydrates that are too acidic lead to hydrolysis of the silyl enol ether, whereas slow exchange limits the ability of catalysis to compete with other processes. Indium(III) chloride is a borderline catalysts by these criteria, but nevertheless is effective. The optimum solvent is 95 5 isopropanol-water. Under these conditions, the reaction is syn selective, suggesting a cyclic TS.63... 

Most corrosion processes in copper and copper alloys generally start at the surface layer of the metal or alloy. When exposed to the atmosphere at ambient temperature, the surface reacts with oxygen, water, carbon dioxide, and air pollutants in buried objects the surface layer reacts with the components of the soil and with soil pollutants. In either case it gradually acquires a more or less thick patina under which the metallic core of an object may remain substantially unchanged. At particular sites, however, the corrosion processes may penetrate beyond the surface, and buried objects in particular may become severely corroded. At times, only extremely small remains of the original metal or alloy may be left underneath the corrosion layers. Very small amounts of active ions in the soil, such as chloride and nitrate under moist conditions, for example, may result, first in the corrosion of the surface layer and eventually, of the entire object. The process usually starts when surface atoms of the metal react with, say, chloride ions in the groundwater and form compounds of copper and chlorine, mainly cuprous chloride, cupric chloride, and/or hydrated cupric chloride. 

Water has also been shown to be essential for the liquid phase polymerization of isobutylene with stannic chloride as catalyst (Norrish and Russell, 87). The rates of reaction were measured by a dilatometric method using ethyl chloride as common solvent at —78.5°. With a mixture consisting of 1.15% stannic chloride, 20 % isobutylene, and 78.8% ethyl chloride, the rate of polymerization was directly proportional to the amount of added water (up to 0.43% of which was added). A rapid increase in the rate of polymerization occurred as the stannic chloride concentration was increased from 0.1 to 1.25% with higher concentrations the rate increased only gradually. It was concluded that a soluble hydrate is formed and functions as the active catalyst. The minimum concentration of stannic chloride below which no polymerization occurred was somewhat less than half the percentage of added water. When the concentration of the metal chloride was less than about one-fifth that of the added water, a light solid precipitated formation of this insoluble hydrate which had no catalytic activity probably explains the minimum catalyst concentration. The addition of 0.3% each of ethyl alcohol, butyl alcohol, diethyl ether, or acetone in the presence of 0.18% water reduced the rate to less than one-fifth of its normal value. On the other hand, no polymerization occurred on the addition of 0.3 % of these substances in the absence of added water. The water-promoted reaction was halved when 1- and 2-butene were present in concentrations of 2 and 6%, respectively. 

Born s ionic radii pertain to the unhydrated ions. Our values for d for the alkali metal chlorides are in the same direction as the degree of hydration (23) of the metal ions of these chlorides as is shown by columns two and three of Table III. Since each of these positive ions is accompanied by a chloride ion bearing... 

Claus propositions were summarized as three statements in his more widely read paper of 1856 42 (1) If several equivalents of ammonia (from two to six) combine with an equivalent of certain metal chlorides, neutral substances are formed, in which the basic property of ammonia has been destroyed and simultaneously the ammonia can be neither detected by the usual methods nor eliminated by double decomposition . (2) If the chlorine in these compounds is replaced by oxygen, strong bases are obtained, whose saturation capacity is always determined by the oxygen equivalents contained in them but not by the number of equivalents of ammonia present in them . (3) The number of equivalents of ammonia entering into these substances is not a random one as is evident from a number of facts, it is determined by the number of equivalents of water contained in the hydrates of the metal oxides which can enter into such compounds along with the ammonia . 

For reviews on the preparation of metal halides see I, vol. 4 104 for the dehydration of metal chloride hydrates with thionyl chloride, refer to I, vol. 5 153. 

A solution of the metal chloride(hydrated or anhydrous) and the cyclophosphazene in the required stoichiometry(metal ligand 1 1 or 1 2) in methanol or methyl ethyl ketone was heated under reflux for... 

Conjugated dienes can be reduced to monoolefins by treatment with hydrogen, hydrated cobalt chloride, potassium cyanide, potassium chloride, sodium hydroxide, and tetramethylammonium chloride or benzyltri-ethylammonium chloride as the phase-transfer catalyst. The hydridopen-tacyanocobaltate anion, HCo(CN)s3, is the probable metal catalyst (47-... 

Most ionic halides dissolve in water to give hydrated metal ions and halide ions. However, the lanthanide and actinide elements in the +3 and +4 oxidation states form fluorides insoluble in water. Fluorides of Li, Ca, Sr, and Ba also are sparingly soluble, the lithium compound being precipitated by ammonium fluoride. Lead gives a sparingly soluble salt PbCIF, which can be used for gravimetric determination of F . The chlorides, bromides, and iodides of Ag1, Cu1, Hg1, and Pbn are also quite insoluble. The solubility through a series of mainly ionic halides of a... 

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