Mercaptokomplexe von Indium(III)

The complexes of In(III) with thioglycolate (HO? CH₂? CH₂? S^?) have been investigated by pH-metric methods. Only the mononuclear species In(SR)_n(3-n)+ (n = 1, 2, 3, 4) are formed (Fig. 1): It was difficult to obtain an accurate value for the first stability constant K₁ because of the high stability of the 1:1-complex and therefore mixtures of KCl-KNO₃ were used to keep up the ionic strength of μ = 0.1. In presence of chloride, the constants K_n are smaller because of the formation of chloro complexes and mixed complexes In(SR)_nCl_i(3-n-1)+ and the stability constants of these have also been determined. The constants for the complexes without coordinated chloride can finally be obtained by an extrapolation (Fig. 2). The problem of the influence of increasing charge on the stability of various complexes of the isoelectronic 4d¹⁰ cations is discussed (Fig. 3).     

Indium(III) coordination compounds

Data on the homo- and heteroleptic coordination compounds of indium(III) with halide, pseudo-halide, and N,O-donor ligands are generalized. Trends in the coordination numbers and coordination polyhedron geometries and the specifics of formation of hybrid polymer structures are considered. 182 references.     

Indium(I) Tetraiodoaluminate,InAlI4

Indium(I) tetraiodoaluminate, InAlI₄, was obtained from the respective molar amounts of In, InI₃ and AlI₃ at 553 K. The crystal structure [monoclinic, P2₁/m (no. 11), a = 713.5(4), b = 1182.2(3), c = 1108.3(6) pm, β = 96.32(6)°, V = 1013.2(8)·10⁶ pm³, Z = 4, R₁ for 981 reflections with I₀>2σ(I₀): 0.0404] contains discrete indium(I) cations and tetraiodoaluminate anions. No evidence was found for a stereochemical activity of the In‐5s² electron pair. InAlI₄ (Person code mP24) represents a new structure type within the ABX₄ structure family.     

Electron-Transfer Processes in Indium(II) Iodide-o-Quinone Systems

Indium(II) iodide reacts with various substituted o-quinones in nonaqueous solution by successive one-electron-transfer reactions to give (SQ)InI(2) products (SQ = semiquinonate radical anion). Electron spin resonance spectroscopy demonstrates the presence of both mono- and diradical species in the reaction mixture. Addition of 4-picoline to a mixture of In(2)I(4) and TBQ (=3,5-di-tert-butyl-o-quinone) in toluene causes the precipitation of the indium(III)-semiquinonate complex (TBSQ)InI(2)(pic)(2) whose structure has been established by X-ray crystallography: space group P&onemacr;, with a = 13.013(3) ?, b = 13.317(3) ?, c = 10.828(5) ?, alpha = 97.71(3) degrees, beta = 107.98(3) degrees, gamma = 103.92(3) degrees, V = 1684.8(1.2) ?(3), Z = 2. Refinement converged at R = 0.051 and R(w) = 0.064 for 5918 reflections at 23 degrees C. The InO(2)N(2)I(2) kernel is pseudooctahedral, and the structure confirms the presence of the semiquinonate ligand. A reaction scheme which incorporates these results is proposed.     

Indium(III)-catalysed aryl sulfonylation reactions

A rapid, high yielding and regioselective process has been developed for the synthesis of biaryl sulfones via sulfonylation reactions catalysed by indium(III) chloride.     

Indium(I) Heptachlorodigallate(III), InGa2Cl7

Indium(I) heptachlorodigallate(III), InGa₂Cl₇, has been obtained from a mixture of In, Bi and GaCl₃ in a melt of [bmim][Al(nftb)₄] under argon at 373 K. The crystal structure of InGa₂Cl₇ [orthorhombic, Pna2₁ (no.33), a = 1185.7(2), b = 891.4(4), c = 1071.6(2) pm, V = 1132.6(3)·10⁶ pm³, Z = 4, T = 298 K, R₁ for 1994 reflections with I₀>2σ(I₀): 0.0692] contains discrete indium(I) cations and Ga₂Cl₇ anions. InGa₂Cl₇ crystallizes isotypic with Ga₃Cl₇ and KGa₂Cl₇. In^I is coordinated by ten chloride anions in an irregular (4+6) mode. No evidence was found for the stereochemical activity of the In‐5s² electron pair.     

铟硼磷酸盐结构中的交叠生长规律研究(英)

Ｓｅｖｅｒａｌ ｉｎｄｉｕｍ ｂｏｒｏｐｈｏｓｐｈａｔｅｓ ｈａｖｅ ｂｅｅｎ ｒｅｐｏｒｔｅｄ ｒｅｃｅｎｔｌｙ, ｉｎｃｌｕｄｉｎｇ ＫＩｎ[ＢＰ_２Ｏ_８(ＯＨ)](Ⅰ) ａｎｄ ＮａＩｎ[ＢＰ_２Ｏ_８(ＯＨ)](Ⅱ)． Ｔｈｅ ｌａｔｔｅｒ ｔｗｏ ｃｏｍｐｏｕｎｄｓ ｗｅｒｅ ｓｙｎｔｈｅｓｉｚｅｄ ｕｎｄｅｒ ｍｉｌｄ ｈｙｄｒｏｔｈｅｒｍａｌ ｃｏｎｄｉｔｉｏｎｓ, ａｎｄ ｈａｖｅ ｔｈｅ ｓａｍｅ ｍｏｌａｒ ｒａｔｉｏ (Ｍ^Ⅰ∶Ｉｎ∶Ｂ∶Ｐ∶Ｏ∶Ｈ) ｉｎ ｍｏｌｅｃｕｌａｒ ｆｏｒｍｕｌａ ｂｕｔ ｗｉｔｈ ｄｉｆｆｅｒｅｎｔ ｓｔｒｕｃｔｕｒｅ ｔｙｐｅｓ． Ｃｏｍｐｏｕｎｄ Ⅰ ｃｒｙｓｔａｌｌｉｚｅｓ ｉｎ ｔｈｅ ｔｒｉｃｌｉｎｉｃ ｓｙｓｔｅｍ ｗｉｔｈ ｓｐａｃｅ ｇｒｏｕｐ P1 (Ｎｏ．２), ａ＝０．５２６３８(４) ｎｍ, ｂ＝０．８４７９１(５) ｎｍ, ｃ＝０．８１４６９(９) ｎｍ, α＝９１．１７４１(７) °, β＝９３．０６１(７) °, γ＝７９．８２３(５) °, Ｖ＝０．３５７３ ｎｍ^３, Ｚ＝２; ｗｈｉｌｅ ｃｏｍｐｏｕｎｄ Ⅱ ｐｏｓｓｅｓｓｅｓ ａ ｍｏｎｏｃｌｉｎｉｃ ｓｔｒｕｃｔｕｒｅ ｗｉｔｈ ｓｐａｃｅ ｇｒｏｕｐ Ｐ２_１／ｎ (Ｎｏ．１４) ｗｉｔｈ ａ＝０．５１７７(１) ｎｍ, ｂ＝１．６８１５(３) ｎｍ, ｃ＝０．７６８４(２) ｎｍ, β＝９４．１０(３) °, Ｖ＝０．６６７２(２) ｎｍ^３, Ｚ＝４． Ｅｉｇｈｔ-ｍｅｍｂｅｒｅｄ-ｒｉｎｇ ａｎｄ ｓｉｘ-ｍｅｍｂｅｒｅｄ-ｒｉｎｇ ａｒｅ ｆｏｒｍｅｄ ｂｙ ａｌｔｅｒｎａｔｉｎｇ ｂｏｒａｔｅ, ｐｈｏｓｐｈａｔｅ ｔｅｔｒａｈｅｄｒａ ａｎｄ Ｉｎ-ｃｏｏｒｄｉｎａｔｉｏｎ ｏｃｔａｈｅｄｒｏｎ ｓｈａｒｉｎｇ ｃｏｒｎｅｒｓ ｖｉａ ｃｏｍｍｏｎ ｏｘｙｇｅｎ ａｔｏｍｓ ｉｎ ｃｏｍｐｏｕｎｄ Ⅰ ａｎｄ Ⅱ ｒｅｓｐｅｃｔｉｖｅｌｙ． Ｔｈｅ ｐｏｌｙｈｅｄｒａ ｉｎ ｔｈｅ ｓｔｒｕｃｔｕｒｅ ａｒｅ ｏｒｉｅｎｔｅｄ ａｌｏｎｇ ｃｅｒｔａｉｎ ｄｉｒｅｃｔｉｏｎ ｔｏ ｆｏｒｍ ａｌｔｅｒｎａｔｉｎｇ ｌａｙｅｒｅｄ ｆｒａｇｍｅｎｔｓ． Ｔｈｅｓｅ ｔｗｏ ｓｔｒｕｃｔｕｒｅ ｔｙｐｅｓ ｃａｎ ｂｅ ｃｏｎｓｉｄｅｒｅｄ ａｓ ｉｎｔｅｒｇｒｏｗｔｈ ｓｔｒｕｃｔｕｒｅｓ, ｗｈｉｃｈ ｃｏｎｓｉｓｔ ｏｆ ｔｈｅ ｓａｍｅ ｌａｙｅｒｅｄ ｆｒａｇｍｅｎｔｓ ｇｒｏｗｉｎｇ ｉｎ ｄｉｆｆｅｒｅｎｔ ｏｒｉｅｎｔａｔｉｏｎｓ． Ｏｔｈｅｒ ｓｔｒｕｃｔｕｒｅ ｉｎｔｅｒｇｒｏｗｔｈ ｐｏｓｓｉｂｉｌｉｔｉｅｓ ａｒｅ ａｌｓｏ ｅｘｐｅｃｔｅｄ ｉｎ ｓｉｍｉｌａｒ ｓｙｓｔｅｍｓ． ＣＳＤ: Ⅰ, ４０９５８３; Ⅱ, ４１３３４３．     

Reactions of Elemental Indium and Indium(I) Bromide with Nickel-Bromine Bonds: Structure of (eta(5)-C(5)H(5))(Ph(3)P)Ni-InBr(2)(O=PPh(3))

The reactions of elemental indium and In(I)Br with the carbonyl-free organonickel complexes (eta(5)-C(5)H(5))(PR(3))Ni-Br (R = CH(3), C(6)H(5)) have been studied in some detail. Either redox reactions to yield the ionic products [(eta(5)-C(5)H(5))(PR(3))(2)Ni][InBr(4)] (2a,b) occurred or the Ni-In bound systems (eta(5)-C(5)H(5))(PPh(3))Ni-InBr(2)(OPPh(3)) (3a) and [(eta(5)-C(5)H(5))(PPh(3))Ni](2)InBr (4) were obtained in good yields. The new compounds were characterized by elemental analysis, NMR, and mass spectrometry. A short Ni-In bond of 244.65(9) pm was found for 3a. Single crystal data for (eta(5)-C(5)H(5))(PPh(3))Ni-InBr(2)(OPPh(3)).THF (3a): triclinic, P1 with a = 1124.9(3), b = 1353.2(4), c = 1476.4(4) pm, alpha = 94.74(2) degrees, beta = 101.78(2) degrees, gamma = 109.64(1) degrees, V = 2044(1) x 10(6) pm(3), Z = 2, R = 0.053 (R(w) = 0.063).     

The Affinity of Gallium(III) and Indium(III) for Nitrogen Donor Ligands

Abstract

Dedicated to Professor Arthur Martell on the occasion of his seventy fifth birthday.

The complexes of In(III) and Ga(III) with a variety of nitrogen donor ligands were studied in aqueous solution by glass electrode potentiometry at 25°C in 0.1 M NaNO₃. The ligands were 2-aminomethylpyri-dine (AMPY), ethylenediamine (EN), N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (THPED), and N,N-bis(2-hydroxyethyl)glycine (BICIN). A variety of mixed ligand complexes of the MLOH type were detected with many of the above ligands as L. The logK₁ values obtained were with Ga(III) 8.40 (AMPY), 7.94 (THPED) 12.72 (EN), and In(III) 7.6 (AMPY), 8.20 (THPED), and 7.06 (BICIN). These formation constants are discussed in relation to previous predictions that In(III) and Ga(III) would have a substantial chemistry with nitrogen donor ligands. Of particular interest is the Ga(III) system with EN, where a very stable Ga(EN)³⁺ complex is formed, but no higher complexes except for hydrolyzed species such as Ga(EN)OH²⁺ and Ga(EN)(OH)₂ ⁺.     

Reaction of Indium with Tricarbonylcyclopentadienyl-molybdenum(II) and -tungsten(II) Chlorides

The reactions of indium with tricarbonylcyclopentadienyl-molybdenum(II) and -tungsten(II) chlorides in donor solvents result in formation of compounds containing Mo-In and W-In bonds. The formalkinetic features of the metal oxidation with ⁵-C₅H₅Mo(CO)₃Cl in dimethylformamide were studied.     

Gallium and Indium Complexes of Bis(amino thiol) (N(2)S(2)) Ligands

Three methods have been developed to prepare gallium and indium complexes of three tetradentate N(2)S(2) ligands of the general formula M(N(2)S(2))R (M = Ga, In; R = Cl, Br, SCN, O(2)CC(6)H(5)-O,O'). The ancillary ligand (Cl, SCN, O(2)CC(6)H(5)-O,O') was varied with the tetradentate ligand BAT-TM. X-ray crystallography shows that the coordination geometry about the d(10) metal ion is influenced by the steric requirements of the ligands. X-ray crystallography of four molecules results in the following data: GaCl(BAT-TM) (1), formula = C(10)H(22)ClGaN(2)S(2), space group = Pnma, a = 12.387(4) ?, b = 21.116(6) ?, c = 5.986(2) ?, V = 1565.8(9) ?(3), Z = 4; InCl(BAT-TM) (2), formula = C(10)H(22)ClInN(2)S(2), space group = Pnma, a = 12.968(9) ?, b = 29.29(1) ?, c = 5.866(2) ?, V = 1620(2) ?(3), Z = 4; InNCS(BAT-TM) (3), formula = C(11)H(24)ClInN(3)S(3), space group = Pbca, a = 11.812(3) ?, b = 11.679(3) ?, c = 24.238(9) ?, V = 3449.7 (17) ?(3), Z = 8; In(O,O'-O(2)CC(6)H(5))(BAT-TM) (4), formula = C(19)H(29)O(2)InN(2)S(2), space group = P2(1)/n, a = 10.783(2) ?, b = 18.708(4) ?, c = 12.335(4) ?, V = 2321.7(9) ?(3), Z = 4. Proton NMR studies show that the complexes are stable in solution; in polar solvents such as acetonitrile, for certain molecules, two metal-ligand complexes are observed. Similarly, two metal-ligand complexes are seen in NMR data taken in 80% acetonitrile/20% D(2)O (pD = 4.6) mixture. HPLC studies (acetonitrile/50 mM sodium acetate, pH = 4.6) show that the lipophilicity of the ligand determines the retention time of the complex.     

三价铟化合物在有机合成中的应用

综述了近年来三价铟化合物促进的多种有机反应及其在有机合成中的应用,其中重点讨论了三价铟化合物促进下的碳-碳键和碳-杂原子键的形成反应.     

Indium(III) complexes with some salicylidene aromaticSchiff bases

In(III) complexes with salicylidene aromaticSchiff bases have been prepared. The nature of the complexes has been studied by microanalysis of the solid complexes, conductometric titration, uv and ir spectrophotometric measurements. The complexes are of the type 11 and 21 [Ligand: In(III)] depending upon theSchiff base. The tendency of the salicylideneSchiff base molecule towards complex formation with In(III) is found to depend largely on the strength of the intramolecular hydrogen bond established between the aldehydic OH group and C=N. Furthermore, it is concluded that theseSchiff bases cordinate to In(III) as tri- or bidentate ligands depending upon the molecular structure of theSchiff base (not as monodentate ligand as previously described). The high molar absorbance of the 12 In(III) complex with salicylidene-o-hydroxyaniline I (17,800 mol^–1 cm²) can be applied for the micro determination of small amounts of Indium as low as 0.57 g/ml solution.

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Indium(III)-Komplexe mit aromatischen Schiff-Basen

Zusammenfassung Es wurden einige In(III)-Komplexe mit (von Salicylaldehyd hergeleiteten)Schiff-Basen hergestellt. Elementaranalyse, konduktometrische Titration und UV- sowie IR-Spektroskopie wurden zur Aufklärung der Komplexe herangezogen. Es werden je nach verwendeterSchiff-Base 11-oder 21-Komplexe gebildet. Die Bildungstendenz der Komplexe mit denSchiff-Basen als drei- oder zweizähnige Liganden hängt weitgehend von Stärke und Ausbildungsmöglichkeit von H-Brückenbindungen ab. Einer der beschriebenen Komplexe ist zur photometrischen Mikrobestimmung von In(III) geeignet.

     

Indium(I) iodide mediated efficient synthesis of selenoglycosides

A convenient odorless methodology has been developed for the preparation of selenoglycosides through indium(I) iodide mediated cleavage of diselenides and reaction with glycosyl bromides. The yields were excellent in all cases. Retention of the configuration at the anomeric center was observed in each case.     

Indium(III) chloride-catalyzed thiolysis of meso-aziridines

Indium(III) chloride efficiently catalyzed the thiol addition to meso-aziridines at very low substrate-catalyst ratios giving rise to 1,2-amino sulfides in excellent yields and complete diastereocontrol.     

Indium(III) bromide-catalyzed hydroarylation of alkynes with indoles

Indium(III) bromide-catalyzed hydroarylation of alkynes with indoles leading to the synthesis of 3-vinylindoles in good to excellent yields was achieved. The E/Z ratio of the products depends on the substituents on the indole. This protocol is efficient and atom-economic from the synthetic point of view.     

Indium(III)-catalyzed hydrative cyclization of 1,7-diynyl ethers

A new hydrative cyclization of 1,7- and 1,8-diynyl ethers is reported. Using catalytic InI(3) and p-TSA as a cocatalyst, several 2,2-disubstituted tetrahydrofurans with exocyclic enone appendages were prepared. Reaction optimization and scope, mechanistic insight, and further transformation to a C-nucleoside analog are presented.     

Polarographie von Indium(III) in Alkali-und Erdalkalinitratlösungen

Zusammenfassung Es wurde das polarographische Verhalten von Indium(III) in verschiedenen Nitraten in Abhängigkeit von der Konzentration untersucht. Die Ergebnisse wurden unter besonderer Beachtung der Faktoren Viskosität, Diffusionskoeffizienten und Ionensolvatation interpretiert. Die scheinbaren Geschwindigkeitskonstanten wurden nach dem Verfahren vonDelahay bestimmt und ein quasireversibles Verhalten festgestellt.

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Polarography of indium(III) in alkali and alkaline earth nitrates

Polarographic behavior of Indium(III) in several nitrates of varying concentrations has been studied and resuts interpreted in the light of factors viscosity, diffusion coefficients and ion solvation. The apparent rate constants were determined byDelahay's treatment which revealed its quasireversible behavior.

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An den allfällige Korrespondenz zu richten ist.     

Indium(III) triflate-catalyzed reaction of 2-carbomethoxycyclobutanone with nitrones

2-Carbomethoxycyclobutanone reacted with N-phenyl-C-arylnitrones to afford methyl 5-oxo-2-[aryl(phenylamino)methyl]tetrahydrofuran-2-carboxylates by the catalysis of indium(III) triflate in the presence of magnesium sulfate.     

Indium(III) chloride-promoted intramolecular addition of allylstannanes to alkynes

In the presence of an equimolar amount of InCl(3), 8-tributylstannyl-6-octen-1-ynes (allylstannanes bearing an alkynyl group) were efficiently cyclized to 2-allyl-1-methylenecyclopentanes. In contrast, catalytic use of InCl(3) gave 2-allyl-1-(tributylstannylmethylene)cyclopentanes mainly by intramolecular allylstannylation. These cyclizations could proceed via intramolecular addition of an allylindium intermediate.