Potassium with metal halides

Ammonium Dioxalato - diammino - chromium, [Cr(NH3)2 (C204)2]NH4.2H20, is obtained in red needles by acting upon dibromo-diaquo-diammino-chromic bromide with aqueous oxalic acid at a temperature of 60° C. The colour changes in solution to dark red and the salt separates. From the ammonium salt other salts may be prepared by treating an aqueous solution with metallic halide. The potassium salt crystallises in red needles containing two molecules of water the sodium salt crystallises in dark red prisms the lithium salt in red needles or leaflets and the caesium salt in dark red needles. These salts are very stable and may be reerystallised from water. 

By far the most frequently used method is the deprotonation with potassium tert-butoxide, which gives the potassium salts in nearly quantitative yields. The method seems to be usable for any bis(chalcogenophosphinyl and -phosphoryl)imide and has been employed for a broad diversity of derivatives, regardless of the nature of the chalcogen.2,26,30,33,36-38,49,89,91,99 If the salts are needed for further use in reactions with metal halides to form complexes, the potassium salt can be used in situ, without isolation, e.g., with zinc(II) chloride or palladium and platinum chloro complexes.41,43 Potassium metal in THF also forms the salt K[SPh2PNPPh2S] in 82% yield, 38 but the method is not practical for preparative purposes. Potassium-crown ether complexes, [K(18-crown-6)][Q1Ph2PNPPh2Q1] with Q1 = O,92 Q1 = S,93 and Q1 = Se,98 have been prepared by direct complexation of the potassium salt with the macrocyclic ligand. 

Ester eliminations are normally one of two types, base catalyzed or pyrolytic. The usual choice for base catalyzed j5-elimination is a sulfonate ester, generally the tosylate or mesylate. The traditional conditions for elimination are treatment with refluxing collidine or other pyridine base, and rearrangement may occur. Alternative conditions include treatment with variously prepared aluminas, amide-metal halide-carbonate combinations, and recently, the use of DMSO either alone or in the presence of potassium -butoxide. 

The reaction of alkyl halides with metal nitrites is one of the most important methods for the preparation of nitroalkanes. As a metal nitrite, silver nitrite (Victor-Meyer reaction), potassium nitrite, or sodium nitrite (Kornblum reaction) have been frequently used. The products are usually a mixture of nitroalkanes and alkyl nitrites, which are readily separated by distillation (Eq. 2.47). The synthesis of nitro compounds by this process is well documented in the reviews, and some typical cases are listed in Table 2.3.92a Primary and secondary alkyl iodides and bromides as well as sulfonate esters give the corresponding nitro compounds in 50-70% yields on treatment with NaN02 in DMF or DMSO. Some of them are described precisely in vol 4 of Organic Synthesis. For example, 1,4-dinitrobutane is prepared in 41 -46% yield by the reaction of 1,4-diiodobutane with silver nitrite in diethyl ether.92b 1-Nitrooctane is prepared by the reaction with silver nitrite in 75-80% yield. The reaction of silver nitrite with secondary halides gives yields of nitroalkanes of about 15%, whereas with tertiary halides the yields are 0-5%.92c Ethyl a-nitrobutyrate is prepared by the reaction of ethyl a-bromobutyrate in 68-75% yield with sodium nitrite in DMF.92d Sodium nitrite is considerably more soluble in DMSO than in DMF as a consequence, with DMSO, much more concentrated solutions can be employed and this makes shorter reaction times possible.926... 

Bis[(tris(isopropyl)cyclopentadienyl)]zinc (Zn C5(Pr1)3H2 2, 21) and bis[(tetrakis(isopropyl)cyclopentadienyl)]zinc (Zn C5(Pr1)4H 2, 22) were synthesized from the respective potassium cyclopentadienides and zinc iodide as shown in Scheme 18.50 The same slipped sandwich compounds were also isolated from zinc-reduced VC13 solutions when they were treated with these alkali metal cyclopentadienides at room temperature.51 The outcomes of these reactions suggest that zincocenes are likely intermediates in the syntheses of transition metal metallocenes, in which the metal halides have been pre-reduced with zinc. The solid-state structure of Zn G5(Pr1)4H 2 is shown in Figure 10. The sole... 

Normal glass will only transmit radiation between about 350 nm and 3 /rm and, as a result, its use is restricted to the visible and near infrared regions of the spectrum. Materials suitable for the ultraviolet region include quartz and fused silica (Figure 2.28). The choice of materials for use in the infrared region presents some problems and most are alkali metal halides or alkaline earth metal halides, which are soft and susceptible to attack by water, e.g. rock salt and potassium bromide. Samples are often dissolved in suitable organic solvents, e.g. carbon tetrachloride or carbon disulphide, but when this is not possible or convenient, a mixture of the solid sample with potassium bromide is prepared and pressed into a disc-shaped pellet which is placed in the light path. 

The results from our work on the reaction of propylene oxide with cobalt carbonyl and base in methanol are given in Table VIII. Several base/metal oxide combinations were evaluated under mild reaction conditions. The difference in activity between the bases was not as pronounced as that observed in the reaction with benzyl halides with the exception of potassium methoxide which, when used alone, gave exclusively the hydroxy ether resulting from methoxide addition to the epoxide ring. However, the activity of sodium... 

A very reactive form of a finely divided metal is a so-called Rieke powder [79]. These materials are produced as fine powders by chemical precipitation during the reduction of various metal halides ivith potassium metal in refluxing tetrahydrofuran. Obviously this is a potentially hazardous laboratory procedure and ultrasound has provided an alternative method of preparation of these extremely valuable reagents [80]. The sonochemical technique involves the reduction of metal halides with lithium in TH F at room temperature in a cleaning bath and gives rise to metal powders that have reactivities comparable to those of Rieke powders. Thus powders of Zn, Mg, Cr, Cu, Ni, Pd, Co and Pb were obtained in less than 40 min by this ultrasonic method compared with reaction times of 8 h using the experimentally more difScult Rieke method (Tab. 3.1). 

Binary Compounds. The thermodynamics of the formation of HfCl2, of HfCl4, fused sodium and potassium chlorides have been described. The reduction of ZrXj (X = Cl, Br, or I) with metallic Zr or A1 in molten AICI3 has been studied at temperatures from 250 to 360 °C, depending on the halide. The electronic spectra of the initial reaction products were consistent with either a solvated Zr complex or an intervalence Zr "-Zr" species. Further reduction resulted in the precipitation of reduction products which were identified by analysis and i.r., electronic, and X-ray powder diffraction spectra. The stability of the trihalides with respect to disproportionation was observed to increase from chloride to iodide thus ZrC and ZrCl2,0.4AlCl3 were precipitated, whereas only Zrlj was formed. ... 

Violent reactions can occur with many metal hahdes. For example, with zinc halides or iron halides, single replacement reactions take place. Such potassium-metal halide mixtures can react violently when subjected to mechanical shock. 

If we take a series of alkali metal halides, all with the rock salt structure, as we replace one metal ion with another, say sodium with potassium, we would expect the metal-halide internuclear distance to change by the same amount each time if the concept of an ion as a hard sphere with a particular radius holds true. Table 1.8 presents the results of this procedure for a range of alkali halides, and the change in internuclear distance on swapping one ion for another is highlighted. 

Rieke reported in the early 1970s the preparation of highly reactive metal forms by the reduction of metal halides with alkali metals19. In the original work, anhydrous ZnBr2 in dry THF was refluxed for 4 h with potassium affording a finely divided slurry of an air-sensitive reactive metal, denoted as Zn (equation 5)43. 

The pellet (pressed-disk) technique depends on the fact that dry, powdered potassium bromide (or other alkali metal halides) can be compacted under pressure in vacuo to form transparent disks. The sample (0.5-1.0 mg) is intimately mixed with approximately 100 mg of dry, powdered KBr. Mixing can be effected by thorough grinding in a smooth agate mortar or, more efficiently, with a small vibrating ball mill, or by lyophili-... 

When iodine is dissolved in hydriodic acid or a soln. of a metallic iodide, there is much evidence of chemical combination, with the formation of a periodide. A. Baudrimont objected to the polyiodide hypothesis of the increased solubility of iodine in soln. of potassium iodide, because he found that an extraction with carbon disulphide removed the iodine from the soln. but S. M. Jorgensen showed that this solvent failed to remove the iodine from an alcoholic soln. of potassium iodide and iodine in the proportion KI I2, and an alcoholic soln. of potassium iodide decolorized a soln. of iodine in carbon disulphide. The hypothesis seemed more probable when, in 1877, G. S. Johnson isolated cubic crystals of a substance with the empirical formula KI3 by the slow evaporation of an aqueous-alcoholic soln. of iodine and potassium iodide over sulphuric acid. There is also evidence of the formation of analogous compounds with the other halides. The perhalides or poly halides—usually polyiodides—are products of the additive combination of the metal halides, or the halides of other radicles with the halogen, so. that the positive acidic radicle consists of several halogen atoms. The polyiodides have been investigated more than the other polyhalides. The additive products have often a definite physical form, and definite physical properties. J. J. Berzelius appears to have made the first polyiodide—which he called ammonium bin-iodide A. Geuther called these compounds poly-iodides and S. M. Jorgensen, super-iodides. They have been classified 1 as... 

The complications which result from the hydrolysis of alkali metal cyanides in aqueous media may be avoided by the use of non-aqueous solvents. The one most often employed is liquid ammonia, in which derivatives of some of the lanthanides and of titanium(III) may be obtained from the metal halides and cyanide.13 By addition of potassium as reductant, complexes of cobalt(O), nickel(O), titanium(II) and titanium(III) may be prepared and a complex of zirconium(0) has been obtained in a remarkable disproportion of zirconium(III) into zirconium(IV) and zirconium(0).14 Other solvents which have been shown to be suitable for halide-cyanide exchange reactions include ethanol, methanol, tetrahydrofuran, dimethyl sulfoxide and dimethylformamide. With their aid, species of different stoichiometry from those isolated from aqueous media can sometimes be made [Hg(CN)3], for example, is obtained as its cesium salt form CsF, KCN and Hg(CN)2 in ethanol.15... 

Alkylation has been carried out with alkyl halides in methanolic alkali metal methoxide,08 103104 112,114 273 in aqueous ethanolic solution of potassium hydroxide and potassium iodide,106 281 and in dimethylforma-mide in the presence of potassium carbonate.114 Alkylation generally led to more than one product. 

Use of the alloy to reduce metal halides in solvents to the finely divided and highly reactive metals is not recommended for cases where the halide is highly soluble in the solvent (e.g. zinc chloride or iron(III) chloride in THF). Explosive reaction may ensue [1]. The alloys explode violently in contact with silver halides. See Potassium Metal halides... 

Salts of the ester 0,0 -diethyl dithiophosphate have been prepared by two different methods. One involves the reaction of (C2H50)2P(S)C1 with potassium hydrogen sulfide.1 The other is the reaction of phosphorus (V) sulfide with ethanol followed by the addition of metal halide.1-3 The second method is the basis for this preparation, although the chromium(III) compound has not previously been reported. Salts of cobalt(III), nickel(II), and lead(II) can be prepared by analogous reactions using cobalt (III) fluoride, nickel(II) chloride 6-hydrate, and lead(I) oxide, respectively. 

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