Pentavalent

Ihese reactions (and those of the irichloride) indicate the great tendency of (pentavalent) phosphorus to unite with oxygen (cf. silicon). 

Figure 2-52. a) Two semipolar resonance structures are needed in a correct VB representation of the nitro group, b) Representation of a nitro group by a structure having a pentavalent nitrogen atom, c) The RAMSES notation of a nitro group needs no charged resonance structures. One jr-system contains four electrons on three atoms. 

Oxygen Octahedra. An important group of ferroelectrics is that known as the perovskites. The perfect perovskite stmcture is a simple cubic one as shown in Figure 2, having the general formula ABO, where A is a monovalent or divalent metal such as Na, K, Rb, Ca, Sr, Ba, or Pb, and B is a tetra- or pentavalent cation such as Ti, Sn, Zr, Nb, Ta, or W. The first perovskite ferroelectric to be discovered was barium titanate [12047-27-7] and it is the most thoroughly investigated ferroelectric material (10). 

It is estimated that mote than 25 x 10 different potentially toxic OP esters can be made using Schrader s classic (27) formula for effective phosphorylating agents, (39), where R and are short-chain alkyl, alkoxy, alkylthio, or alkylamino groups, and X is a displaceable moiety with a high energy P-bond such as E or acyl anhydride, and the pentavalent phosphoms atom is bonded to oxygen or sulfur. 

The most important manganese(V) compound is K MnO, a key intermediate in the manufacture of potassium permanganate. Potassium manganate(V) is an easily crystallized salt obtained by reduction of potassium permanganate using sodium sulfite in strong sodium hydroxide solution. This was the first compound to be recognized as exclusively pentavalent. 

Niobium Halides and Oxyhalides. AH possible haUdes of pentavalent niobium are known and preparations of lower valent haUdes generally start with the pentahaUde. Ease of reduction decreases from iodide to fluoride. 

Tri- and pentacoordinate phosphoms compounds often react by electron-pair mechanisms as demonstrated by the nucleophilic reactivity of the lone pair electrons in trivalent compounds, and the electrophilicity of the phosphoms atom in the pentavalent compounds. Some compounds also react by free-radical mechanisms. The theoretical and synthetic aspects of the chemistry of phosphoms compounds have been described (6—9). 

Phosphoms haUdes and metals or metal salts form addition complexes. Some typical compounds are PCl iSbCl and PCl iAlCl. The trivalent complexes contain metal—phosphoms bonds. The pentavalent complexes involve rearrangements to produce assembles of tetrahedral PX cations and various anions. 

Pentavalent phosphorus derivatives can be converted to phosphonyl halides or phosphine oxides by partial hydrolysis or by other oxygen donors. 

The reactions are general for chlorine and bromine. Iodine does not react to form pentavalent phosphoms compounds. Fluorides are best formed with less active fluorinating agents. 

Rhenium Halides and Halide Complexes. Rhenium reacts with chlorine at ca 600°C to produce rheniumpentachloride [39368-69-9], Re2Cl2Q, a volatile species that is dimeric via bridging hahde groups. Rhenium reacts with elemental bromine in a similar fashion, but the metal is unreactive toward iodine. The compounds ReCl, ReBr [36753-03-4], and Rel [59301-47-2] can be prepared by careful evaporation of a solution of HReO and HX. Substantiation in a modem laboratory would be desirable. Lower oxidation state hahdes (Re X ) are also prepared from the pentavalent or tetravalent compounds by thermal decomposition or chemical reduction. 

Salts containing pentavalent tungsten may be obtained by the reduction of alkaU tungstate in concentrated hydrochloric acid. Salts of types M(I)2(W0C1 ) (green), M(I)(WOCl (brown-yeUow), and M(I)(WOCl 2 ) h ve been isolated. Thiocyanato and bromo salts are also known. 

Salts containing tetravalent tungsten have been prepared by various methods. The most important are the octacyanides, M(I)4(W(CN)g), which form yellow crystals and are very stable. They are isolated as salts or free acids and can be oxidized by KMnO in H2SO4 to compounds containing pentavalent tungsten, M(I)2(W(CN)g) (yellow). 

Vanadium Sulfates. Sulfate solutions derived from sulfuric acid leaching of vanadium ores are industrially important in the recovery of vanadium from its raw materials. Vanadium in quadrivalent form may be solvent-extracted from leach solutions as the oxycation complex (VO) ". Alternatively, the vanadium can be oxidized to the pentavalent form and solvent-extracted as an oxyanion, eg, (V O ) . Pentavalent vanadium does not form simple sulfate salts. 

For solvent extraction of pentavalent vanadium as a decavanadate anion, the leach solution is acidified to ca pH 3 by addition of sulfuric acid. Vanadium is extracted in about four countercurrent mixer—settler stages by a 3—5 wt % solution of a tertiary alkyl amine in kerosene. The organic solvent is stripped by a soda-ash or ammonium hydroxide solution, and addition of ammoniacal salts to the rich vanadium strip Hquor yields ammonium metavanadate. A small part of the metavanadate is marketed in that form and some is decomposed at a carefully controlled low temperature to make air-dried or fine granular pentoxide, but most is converted to fused pentoxide by thermal decomposition at ca 450°C, melting at 900°C, then chilling and flaking. 

For vanadium solvent extraction, Hon powder can be added to reduce pentavalent vanadium to quadrivalent and trivalent Hon to divalent at a redox potential of —150 mV. The pH is adjusted to 2 by addition of NH, and an oxyvanadium cation is extracted in four countercurrent stages of mixer—settlers by a diesel oil solution of EHPA. Vanadium is stripped from the organic solvent with a 15 wt % sulfuric acid solution in four countercurrent stages. Addition of NH, steam, and sodium chlorate to the strip Hquor results in the precipitation of vanadium oxides, which are filtered, dried, fused, and flaked (22). Vanadium can also be extracted from oxidized uranium raffinate by solvent extraction with a tertiary amine, and ammonium metavanadate is produced from the soda-ash strip Hquor. Fused and flaked pentoxide is made from the ammonium metavanadate (23). 

In 1912, however, (201) it was discovered that espundia (American mucocutaneous leishmaniasis) can be cured by tartar emetic. It was soon learned that kala-a2ar (visceral leishmaniasis) and oriental sore (a cutaneous form of the disease occurring in the Middle East) also respond to antimonial therapy, especially when compounds of pentavalent antimony are employed. Treatment of leishmaniasis with the latter type of antimonials is safe and effective in over 90% of the cases (202). In 1918, it was demonstrated that tartar emetic is of value in the treatment of schistosomiasis (203). Pentavalent antimonials proved to be less effective. The introduction of antimony compounds for the treatment of parasitic diseases is undoubtedly one of the important milestones in the history of therapeutics (see Antiparasitic agents). 

Meglumine [6284-40-8] antimonate [133-51 -7] C H NO HO Sb, (Glucantime) is a pentavalent antimonial used for the treatment of leishmania sis in Latin America (207) and in the French-speaking areas of Europe and Africa (206). It is adrxiinistered by deep intramuscular injection. Although relatively safe and usually well tolerated, numerous side effects have been observed. It is not available in the United States. 

Antimony compounds have been used to treat leishmaniasis ever since tartar emetic (antimony potassium tartrate) was discovered early in the 20th century to have efficacy against the mucocutaneous form of the disease. The cutaneous form has been treated with tartar emetic formulated in an ointment. Many side effects have been seen with this trivalent antimonial, some of which can be ascribed to the difficulty of obtaining pure antimony for its manufacture. These side effects include toxicity to the heart, Hver, and kidneys. Other promising trivalent antimonials have been abandoned in favor of pentavalent antimonials with lower toxicity. 

Cation is water repellent based on pentavalent nitrogen... 

The silyl group directs electrophiles to the substituted position. That is, it is an ipso-directing group. Because of the polarity of the carbon-silicon bond, the substituted position is relatively electron-rich. The ability of silicon substituents to stabilize carboca-tion character at )9-carbon atoms (see Section 6.10, p. 393) also promotes ipso substitution. The silicon substituent is easily removed from the c-complex by reaction with a nucleophile. The desilylation step probably occurs through a pentavalent silicon species ... 

Perfluorinated organic bromides can be oxidatively fluonnated with elemental fluorine to derivatives containing tn- [124] and pentavalent [/25 126 127] bromine in yields up to 42% Perfluoroheptylbromine tetrafluoride has been used to fluonnate double bonds in halogenated alkenes [127]... 

Compounds of tnvalent phosphorus are generally oxidized to pentavalent phosphorus denvaPves bis(fluoroalkyl) and tns(fluoroalkyl) phosphites are oxi dized to the corresponding[106, lOI] (equation 92)... 

The Arbuzov reaction,also called the Michaelis-Arbuzov reaction, allows for the synthesis of pentavalent alkyl phosphoric acid esters 4 from trivalent phosphoric acid esters 1 (Z,Z = R,OR) by treatment with alkyl halides 2. 

Recent mechanistic studies have shown that the many combinations of alcohols, carboxylic acids and solvents cannot be correctly described by a uniform mechanism. In certain cases the reaction appears to involve a pentavalent dialkoxyphos-phorane 10 as an intermediate, which is in equilibrium with oxyphosphonium salt 8 4 ... 

Funftel, n. fifth, fifth part, fiinfwertig, a. quinquevalent, pentavalent. Funfwertigkeit, /. quinquevalence, pentava-lence. 

The introduction of divalent calcium and barium oxides into frits in preference to monovalent sodium and potassium generally increases water resistance. Furthermore, oxides of tetravalent and pentavalent metals have a favourable effect on the resistance of glasses and enamels to water. The influence of B2O3 and fluorine in the frit upon chemical resistance is variable and is dependent upon the content of them and the balance of the frit constituents, but they usually cause a diminution in resistance. In general, mill-added clay, silica and opaciher increase water resistance provided the firing or fusing of the enamel is at the optimum. 

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