Aluminum thallium oxide

Unlike boron, aluminum, gallium, and indium, thallium exists in both stable univalent (thaHous) and trivalent (thaUic) forms. There are numerous thaHous compounds, which are usually more stable than the corresponding thaUic compounds. The thaUium(I) ion resembles the alkaU metal ions and the silver ion in properties. In this respect, it forms a soluble, strongly basic hydroxide and a soluble carbonate, oxide, and cyanide like the alkaU metal ions. However, like the silver ion, it forms a very soluble fluoride, but the other haUdes are insoluble. Thallium (ITT) ion resembles aluminum, gallium, and indium ions in properties. 

Haapakka and Kankare have studied this phenomenon and used it to determine various analytes that are active at the electrode surface [44-46], Some metal ions have been shown to catalyze ECL at oxide-covered aluminum electrodes during the reduction of hydrogen peroxide in particular. These include mercu-ry(I), mercury(II), copper(II), silver , and thallium , the latter determined to a detection limit of <10 10 M. The emission is enhanced by organic compounds that are themselves fluorescent or that form fluorescent chelates with the aluminum ion. Both salicylic acid and micelle solubilized polyaromatic hydrocarbons have been determined in this way to a limit of detection in the order of 10 8M. 

This section will focus on homonuclear neutral or anionic clusters of the elements aluminum, gallium, indium, and thallium, which have an equal number of cluster atoms and substituents. Thus, they may clearly be distinguished from the metalloid clusters described below, which in some cases have structures closely related to the allotropes of the elements and in which the number of the cluster atoms exceeds the number of substituents. The compounds described here possess only a single non-centered shell of metal atoms. With few exceptions, their structures resemble those of the well-known deltahedral boron compounds such as B4(CMe3)4 [30], B9CI9 [31] or [B H ]2 [32]. The oxidation numbers of the elements in these... 

Other metah—a classification given to seven metals that do not fit the characteristics of transition metals. They do not exhibit variable oxidation states, and their valence electrons are found only on the outer shell. They are aluminum, gallium, indium, tin, thallium, lead, and bismuth. 

The oxidizing properties of thallium(III) in both aqueous and non-aqueous media obviously preclude the existence of a number of compounds analogous to those found for aluminum, gallium and indium in this oxidation state. Thus, while there is much richer chemistry for thallium in the +1 state, there is a concomitant decrease in the detailed information on thallium(III) coordination chemistry. 

Thallium is the heaviest member of the Group 13 elements. Aluminum is also a member of that group, and its chemistry is dominated by the +3 oxidation state. Thallium, however, is found most usually in... 

NMO NMP Nu PPA PCC PDC phen Phth PPE PPTS Red-Al SEM Sia2BH TAS TBAF TBDMS TBDMS-C1 TBHP TCE TCNE TES Tf TFA TFAA THF THP TIPBS-C1 TIPS-C1 TMEDA TMS TMS-C1 TMS-CN Tol TosMIC TPP Tr Ts TTFA TTN N-methylmorpholine N-oxide jV-methyl-2-pyrrolidone nucleophile polyphosphoric acid pyridinium chlorochromate pyridinium dichromate 1,10-phenanthroline phthaloyl polyphosphate ester pyridinium p-toluenesulfonate sodium bis(methoxyethoxy)aluminum dihydride (3-trimethylsilylethoxy methyl disiamylborane tris(diethylamino)sulfonium tetra-n-butylammonium fluoride f-butyldimethylsilyl f-butyldimethylsilyl chloride f-butyl hydroperoxide 2,2,2-trichloroethanol tetracyanoethylene triethylsilyl triflyl (trifluoromethanesulfonyl) trifluoroacetic acid trifluoroacetic anhydride tetrahydrofuran tetrahydropyranyl 2,4,6-triisopropylbenzenesulfonyl chloride 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane tetramethylethylenediamine [ 1,2-bis(dimethylamino)ethane] trimethylsilyl trimethylsilyl chloride trimethylsilyl cyanide tolyl tosylmethyl isocyanide meso-tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium trifluoroacetate thallium(III) nitrate... 

Compounds containing E-E single bonds between the heavier elements of Group 13 received considerable interest in the last decades and developed to a broad field in current organoelement chemistry with a multitude of different formulas and types of structures. The first synthesis of a tetraalkyldielement(4) derivative in 1988 marked the starting point for many aspects of that chemistry and influenced the further development of organoelement chemistry with aluminum, gallium, indium, and thallium in unusual oxidation states to a considerable extent. Some of the first cluster... 

There is also a pronounced tendency for the Group IIIA metals to form metal-metal bonds and bridged structures. The electron configuration ns2 np1 suggests the possible loss of one electron from the valence shell to leave the ns2 pair intact. The electron pair that remains in the valence shell is sometimes referred to as an inert pair, and a stable oxidation state that is less than the group number by two units is known as an inert pair effect. The fact that oxidation states of +2, +3, +4, and +5 occur for the elements in Groups IVA, VA, VIA, VIIA, respectively, shows that the effect is quite common. Thus, it will be seen that the Group IIIA metals other than aluminum have a tendency to form +1 compounds, especially thallium. 

Aluminum, gallium, and thallium form mixed oxides with other metals. First, there are aluminum oxides containing only traces of other metal ions. These include ruby (Cr3+) and blue sapphire (Fe2+, Fe3+, and Ti4+). Synthetic ruby, blue sapphire, and gem-quality corundum are now produced synthetically in large quantities. Second, there are mixed oxides containing macroscopic proportions of other elements, such as spinel (MgAl204) and crysoberyl (BeAl204). 

Thallium has two important oxidation states, Tl (-El) and Tl (+3). The trivalent form more closely resembles aluminum and the monovalent form more resembles alkali metals such as potassium. The toxic nature of the monovalent Tl is due to its similarity to potassium in ionic radius and electrical charge. Thallium sulfate use as a pesticide was restricted in 1965 in the USA and the World Health Organization (WHO) recommended in 1973 against its use as a rodenticide due to its toxicity (WHO, 1973). From 1912 to 1930, thallium compounds were used extensively for medicinal purposes for example in the treatment of ringworm (because of the depilatory effects), dysentery, and... 

Later, this cycloaddition reaction was improved by the pretreatment of the enamide ester with an equimoler amount of trialkylsilyl trifluoromethanesul-fonate and triethylamine at ambient temperature. The synthesis of tyro-phorine (119) was achieved by the above improved method (Scheme 55). The enamide ester 441 was subjected to annulation using t-butyldimethylsilyl triflate and triethylamine at 15°C to produce the bicyclic lactam 442 in 68% yield. Oxidation of 442 with thallium(III) trifluoroacetate and boron triflu-oroetherate in a mixture of dichloromethane and trifluoroacetic acid at 4°C produced (83%) the pentacyclic compound 443. Hydrolysis of 443, followed by decarboxylation of the resultant acid, gave the pentacyclic lactam 444. Reduction of 444 with sodium bis(2-methoxyethoxy)aluminum hydride in refluxing dioxane afforded tyrophorine (119) (85CC1159). 

---