Oxochloride

About 80-90% of the elemental P produced is reoxidized to (pure) phosphoric acid (p. 521). The rest is used to make phosphorus oxides (p. 503). sulfides (p. 506), phosphorus chlorides and oxochloride (p. 4%). and organic P compounds. A small amount is convened to red phos rftorus (see below) for use in the striking surface of matches for pyrotechnics and as a flame retarding agent (in polyamides). Bulk price for P4 is S2.00/kg. 

Dirheniumheptoxide 2154 is converted by TCS 14, in the presence of 2,2 -dipyri-dine, into the dipyridine complex 2160 [77]. Free ReCls, NbCls, and WCI5 react with HMDSO 7 and 2,2 -bipyridine to form bipyridine oxochloride complexes 2161 and TCS 14, with reversal of the hitherto described reactions of metal oxides with TCS 14. The analogous Mo complex 2162 undergoes silylahon-amination by N-trimethylsilyl-tert-butylamine 2163 to give the bis-imine complex 2164 and HMDSO 7 [77] (Scheme 13.22). 

Early attempts by Asinger to enlarge the scope of hydroalumination by the use of transition metal catalysts included the conversion of mixtures of isomeric linear alkenes into linear alcohols by hydroalumination with BU3AI or BU2AIH at temperatures as high as 110°C and subsequent oxidation of the formed organoaluminum compounds [12]. Simple transition metal salts were used as catalysts, including tita-nium(IV) and zirconium(IV) chlorides and oxochlorides. The role of the transition metal in these reactions is likely limited to the isomerization of internal alkenes to terminal ones since no catalyst is required for the hydroalumination of a terminal alkene under these reaction conditions. 

Before the availability of high-purity lanthanide metals, the most popular starting material was the oxide, readily available pure. Because of their high stability, the oxides cannot readily be converted into the respective trihalides simply by reaction with chlorine or hydrogen chloride as oxochlorides are formed nevertheless, Templeton and Carter (45) have prepared pure trichlorides using this method. 

Hproblems associated with all the trihalides of this review of the presence of small amounts of hydrates or oxochlorides. While on the matter of possible impurities, it may be recalled that in Bommer and Hohmann s early work there is a discrepancy between enthalpies of solution of anhydrous trichlorides and of respective metals in hydrochloric acid. Here the more likely impurity to be responsible is unreacted potassium metal in the lanthanide metal used in the hydrochloric acid dissolution experiments. 

Tellurium tetrachloride is instantaneously hydrolysed by water, giving tellurium oxochloride, which is soluble in concentrated hydrochloric acid, forming HTeCl and HjTeClg. 

When heated in the presence of water vapor, lanthanum oxochloride is formed ... 

Heating with glass at elevated temperatures also forms oxochloride ... 

Because reactions are accompanied by the formation of oxochlorides (the derivatives of the most acidic phenols being the only exception) with partial substitution of chlorine atoms by alkoxide groups, they should be avoided in synthesis of metal alkoxides. 

Mn02Cl2 Least stable of oxochlorides—decomposing at — 30°C. Brown solutions in CC14.755... 

The anhydrous chlorides cannot generally be obtained simply by heating the hydrates because these lose hydrochloric acid (to give the oxochlorides, LnOCl)... 

This is the principal state for Pa, whose chemistry resembles that of Nbv and Tav. For Uv, Npv, Puv, and Amv, however, there is no particular resemblance to Nbv and Tav because of the importance of the An02 ions. Comparatively few solid Anv compounds, other than those of Pav and Puv are known the most notable are the Uv halides, the pentafluorides PaF5, NbF5, and UF5, fluoro anions, namely, AnF[Pg.1137]

Chlorination of 2-(pyrrol-l-yl)pyrrole 330 with sulfuryl dichloride gave the natural 2,3,4-trichloro-l-methyl-5-(perchloropyrrol-l-yl)pyrrole (Ql) 331 in 16% yield (Scheme 74) <2002AGE1740>. Treatment of l-(pyrrol-2-yl)dihy-dropyrrole-2,5-dione 329 with PCls at 55°C gave l-(l-methyl-3,4,5-trichloropyrrol-2-yl)dihydropyrrole-2,5-dione 332. Treatment of compound 329 with a mixture of phosphorus pentachloride and phosphorus oxochloride at 100 °C provided Ql in a yield of 7%. 

Imidazoles have also been prepared by thermal or catalyzed cyclization of N-formyl-j8-imines using phosphorous pentachloride or phosphorous oxochloride and are reviewed (1). 

Though the structures of a tellmium oxochloride and oxobromide have also been reported, their chemistry is not as well-established as that of oxyfluorides. In addition, some organic species, like (n-Pr4N)[TeCLi(OH)], are known. 

Neutral and Cationic Species Containing the FO + Unit. This unit is found in the oxohalides VOX3 (X = F, Cl, Br) and the nitrate, [V0(N03)3], that has a distorted pentagonal bipyramidal stmcture with overall Cs symmetry in the gas phase. The oxochloride, VOCI3, forms a number of addition complexes of the type [VOCbLn] with monodentate (n = 1) or bidentate (n = 2) 0-, S-, or N-donor ligands. ... 

Summary Types of heterolytic reactions with the participation of the silica surface sites are examined. Chemisorption regularities of the organosilicon compounds, cotaining trimethylsilyl group (trimethylhalo- and trimethylpseudohalosilanes), in reaction with surface silanols of fumed silica are analyzed. Peculiarities of surface reactions with the participation of some chlorides and oxochlorides are discussed Some examples of the addition reactions are considered. 

Table 2. Structure of intermediate surface compounds and the products of elimination in reactions of some chlorides and oxochlorides with isolated silanol groups.

In all these reactions the formation of the =SiCI groups and elimination of the appropriate relatively volatile oxochlorides were discovered. It would be interesting in the fiiture to determine the factors, which govern stability of the chemical compounds formed in such a case. 

Reaction of WC16 with salicylic acid produced an oxochloride complex with evolution of gaseous HC1 as mentioned in Section 4.8.2.1.1. Reaction of WOCl4 with 3 equiv. of salicylic acid gave the fi-oxo dimer, [W(=0)(Hsal)(sal)]20.16... 

With poor statistics the problem is the accuracy of the experimental r)c. It is demonstrated by the analysis [30] of the studies of seaborgium oxochloride reported in [31-33]. Figure 6.3 shows some relevant data from these papers. The experimental point at 350 °C for Sg is actually the sum of the measurements at 300, 350 and 400 °C placed at the average 350 °C (in Fig. 6.3, this temperature range is indicated by the horizontal bar). The smooth curves (they correspond to Eq. 6.7) were obtained by Monte Carlo simulations based on principles presented in Sect. 4.2. They are supposed to be the best fits to the data. 

In a recent, and very exciting, publication, it has been shown by Hussey and coworkers [1977a] that phosgene will react in situ with a solution of [TiOCl ] " in room-temperature halogenoaluminate ionic liquids, such as AIQ 3-[emim]Cl ([emim] = l-methyl-3-ethyl-imidazolium cation), and completely and rapidly convert the oxochloride complex into... 

The mechanism of this last step must also be more complicated than it appears, since it is second-order in aluminium oxochloride concentration. A dimeric intermediate was postulated [1842] ... 

This process seems to take place because of the extremely strong acidic properties of Mo03. The cation particle Mo02+ adds chloride ions forming the oxochloride Mo02C12 which is volatile under the experimental conditions, and evaporates from the chloride melt as white smoke... 

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