Indium oxidative addition

In films generated in oxygen plasma, the contribution of arsenic oxides exceeds that of indium oxides. Addition of NF3 gas to oxygen plasma results in a strong shift in synthesis towards formation of indium and arsenic fluorides. All indium in the film is combined with fluorine, and the arsenic peak is a superposition of several components -arsenic oxyfluorides. Composition of the generated film also includes nitrogen. 

The most widely used preparative method of allylindium(m) or propargylindium(lll) compounds is the oxidative addition of metallic indium or indium(l) halides to allylic or propargyl substrates.4 26 27 Allylic bromides and iodides serve as good allylic sources without any other activation. In the case of allylic chlorides, a proper additive such as lithium iodide is required to promote the oxidative addition. Allylic indium compounds prepared by oxidative addition of metallic indium are considered to exist as the sesquihalide structure (allyl jImXj), which has been... 

Synthesis of indium(III) thiolates containing halide donors have also been reported. The oxidative addition reactions of InX (X = C1, Br, I) with PhSSPh yields (PhS)2lnX." Related selenolates can also be synthesized, using PhSeSePh instead of PhSSPh. ... 

K —n-Cyp2y+ 1 (y = 1, 2, 3, 4, 6), FC3F7, CeFs) and CeFsBr react with indium metal in polyethers or THF to generate oxidative addition products of the general formula RfInX (X = C1, Br) involving In(II)." ... 

The mixed-valent gold indium cluster [Au3ln3Cl6(dppe)2] is composed of In(I) and In(II) atoms. Synthetic details were presented in an earlier section. Insertion and redox reactions of In(I) halides have been described. For example, oxidative addition reactions of InX (X = Cl, Br, I) with PhSSPh yields indium(III) thiolates of the type (PhS)2lnX." Unexpected In(II) or In(III) products are common in reactions involving indium(I) halides, which result from facile disproportionation processes. Several such cases were described with divalent indium compounds. 

Indium (I) derivatives of aromatic diols and benzoquinones undergo facile oxidative addition of I2, yielding In(III) products and providing proof of the formation of the low-valent species during synthesis. 

Reaction of indium monobromide or monoiodide with a range of RX (X = Br or I) proceeds within 24 h at RT, in good yield, via oxidative addition - ... 

In the past decade much effort in organoindium chemistry has been devoted to study of carbonyl allylation and aUylindation of carbon-carbon multiple bonds with allylic indium reagents. Apart from the conventional transmetalation of allyl-lifhium or aUyl Grignard reagents with indium(III) halides, a method widely used for preparation of allyhndium(III) compounds is the oxidative addition of metallic indium or indium(I) iodide to aUyhc substrates [3, 6]. Transmetalation of allylstan-nane with indium(III) chloride also gives allylindium(III) [7]. Allylindium(I) was recently prepared by transmetalation of allylmercury with metallic indium in water this compound is regarded as an intermediate in the allylation of carbonyl compounds in aqueous media [8]. A new method of preparation of allylic in-dium(III) reagents - reductive transmetalation of a 7r-allylpalladium(ll) complex with indium(I) salts has been reported this enables the use of a wide variety of allylic compounds and solvents [9]. 

Indium dibromide and MeBr undergo a similar oxidative addition to form MeInBr2 and InBrj. However, the products are difficult to separate, making the method of little practical synthetic value. ... 

Cooper et al. reported that the cascade reaction of the palladium-catalyzed cyclization and the Barbier-type allylation of the 1,3-diene-aryl iodide 514, the aldehydes 515, and indium gave the heterocycles 516 in good yields (Scheme 154).220b The reaction proceeds through oxidative addition of a C—I bond of 514 to Pd(0) and subsequent insertion of a double bond of 517 to give the jr-allylpalladium intermediate 518. Transmetalation of the jr-allylpalladium 518 with indium leads to the allylindium complex 519, and the following reaction with the aldehydes 515 gives 516. 

The kinetics of the deposition of In20i films have not been investigated by many groups, since most of them concentrate on the physical properties and possible applications. The published results are listed in Table 3-8. In addition, there are only two remarks about decomposition pathways. Maruyama andTabata [111] state that indium acetate needs no oxygen as reactant to form indium oxide, i.e., some of the metal-oxygen bonds are not broken during the deposition. Also, as proposed by Nomura and coworkers [122], the butylindium thiolate decomposes via formation of indium sulfides ... 

Specialized methods include (a) reaction of halogens with Rain to yield R InX3 compounds, and (b) reaction of an indium (I) or indium (II) halide with an organic halide via Oxidative Addition (equations 17-18)... 

The oxidative addition of alkanes with formation of alkyl hydride complexes was first demonstrated directly in studies using indium complexes [14], Thus the iridium dihydride derivative Cp lr(H)jPMe3 (Cp = pentamethylcyclopenta-dienyl) after irradiation in solution in cyclohexane or neopentane, produces the complexes Cp (PMe3)Ir(H)(C6Hn) and Cp (PMe3)Ir(H)CH2CMe3 in a satisfactory yield. Other saturated hydrocarbons and benzene also readily add to an iridium complex. 

In some cases a coordinatively unsaturated species and then a product of oxidative addition can be formed via a rearrangement of the complex molecule without elimination of any particles (e.g., olefin complex IV-5 may be converted into the t-allyl hydride derivative IV-6 in Scheme IV. 11 [20c]). Analogously, photolysis of butadiene indium complex IV-7 gives rise to the formation of a hydrido-allyl isomer IV-8 [20d]. 

The metal atom substitutes only the meta and para positions of the benzene ring. In the case of X = NH2, only the meta isomer is formed. The authors propose that the reaction proceeds as DMSO is replaced by the arene with subsequent oxidative addition of the C-H bond to indium to produce an iridium(IV) derivative. Then reductive elimination of methane and addition of DMSO gives the final product. A synchronous elimination of methane and addition of the arene cannot be ruled out however. 

Oxides are normally stable at the operating temperatures necessary to enhance the interaction between their surface and the gas phase, much more stable compared to organic materials. They are normally operated between 500 and 800 K where the conduction is electronic and oxygen vacancies are doubly ionized. Different oxides have been proposed for conductometric chemical sensors, the most studied is by far tin dioxide that has also been commercialized in form of thick film sensors. Other oxides studied are titanium oxide, tungsten oxide, zinc oxide, indium oxide and iron oxide, first in form of thick and then in form of thin films. Furthermore, the use of mixed oxides, as well as the addition of noble metals, has been studied to improve not only selectivity but also stability. 

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