Organometallische Alkoxo–Indium‐Käfigverbindungen

Compounds with Organometallic Alkoxo–Indium Cages The reaction of InMe₃ with PhCH₂OH (molar ratio 1 : 2) at 20 °C in toluene gives the tetranuclear complex [In{(PhCH₂O)₂InMe₂}₃] ( 2 ) in good yield. A further reaction under reflux conditions was not observed. However, at 160 °C in PhCH₂OH a reaction could be realized, which forms an O‐centred corner‐cutted rhombic dodecahedron, [(MeIn)₅(OCH₂Ph)₈(O)] ( 3 ), under evolution of methane. This In–O skeleton can be degraded with elemental cesium to a hexa‐ and heteronuclear complex [Cs{Cs(THF)}{[MeIn(OCH₂Ph)₂]₄O}] ( 4 ). 2 – 4 were characterized by IR, RE, NMR and MS techniques as well as by X‐ray analyses. According to them 2 can be described as In³⁺ ion, coordinated by three metalate units [Me₂In(OCH₂Ph)₂]^–. 3 loses one MeIn fragment during the transfer of two electrons. Two Cs⁺ ions complete the new rhombic dodecahedron, at which different coordination spheres were observed. One Cs⁺ ion possesses additional contacts to a THF ligand and four π‐electron systems from four phenyl rings, while the THF ligand is missing in the environment of the second alkali cation.     

[PtIn6][GaO4]2 – das erste Oxid mit [PtIn6]‐Oktaedern. Darstellung,Charakterisierung und Rietveldverfeinerung – mit einer Bemerkung zur Mischkristallreihe [PtIn6][GaO4]2–x[InO4]x (0 < x ≤ 1)

[PtIn₆][GaO₄]₂ – The First Oxide Containing [PtIn₆] Octahedra. Preparation, Characterisation, and Rietveld Refinement – With a Remark to the Solid Solution Series [PtIn₆][GaO₄]_2‐x[InO₄]_x (0 < x ≤ 1) The novel oxides [PtIn₆][GaO₄]_2–x[InO₄]_x (0 < x ≤ 1) are formed by heating intimate mixtures of Pt, In, In₂O₃, and Ga₂O₃ in the corresponding stoichiometric ratio in corundum crucibles under an atmosphere of argon (1220 K, 70 h). The compounds are black, stable in air at room temperature, reveal a semiconducting behaviour, and decompose only in oxidizing acids. X‐ray powder diffraction patterns can be indexed by assuming a face centered cubic unit cell with lattice parameters ranging from a = 1001.3(1) pm (x = 0) to a = 1009.3(1) pm (x = 1). According to a Rietveld refinement [PtIn₆][GaO₄]₂ crystallizes isotypic to the mineral Pentlandite (Fm3m, Z = 4, R(profile) = 6.11%, R(intensity) = 3.95%). The characteristic building units are isolated [PtIn₆]¹⁰⁺ octahedra which are linked via [GaO₄]^5– tetrahedra to a three dimensional framework. Starting from [PtIn₆][GaO₄]₂ the substitution of Ga³⁺ ions by larger In³⁺ ions leads to the formation of a solid solution series according to the general formula [PtIn₆][GaO₄]_2–x[InO₄]_x and becomes apparent in an increase of the lattice parameter.     

Silicophosphates of Rhodium and Indium

Single crystals of Rh(Si₂O)(PO₄)₃ and In₄(Si₂O) · (PO₄)₆ were prepared by chemical transport reactions in silica tubes and their structures were determined. Crystal data of Rh(Si₂O)(PO₄)₃: trigonal, space group P 3 c1, a = 8.088(3) Å, c = 8.740(2) Å, Z = 2, R(F²) = 0.0379, R_w(F²) = 0.0518 for 601 unique reflections. In₄(Si₂O)(PO₄)₆: hexagonal, space group P6₃/m, a = 8.5149(10) Å, c = 7.7481(12) Å, Z = 1, R(F²) = 0.0436, R_w(F²) = 0.0522 for 509 unique reflections. Both of the compounds have hexagonal close packed array of phosphate groups with metal atoms and SiOSi units in the octahedral interstices, where the SiOSi units show occupational disorder. The structure of the indium compound is considered to be a disordered structure of the reported Mo₄Si₂P₆O₁₃ structure, and contains confacial bioctahedral units.     

Abläufe der Ammonolysen der Ammoniumhexafluorometallate des Aluminiums,Galliums und Indiums, (NH4)3MF6 (M = Al,Ga, In)

The Courses of the Ammonolyses of the Ammonium Hexafluorometalates of Aluminum, Gallium, and Indium, (NH₄)₃MF₆ (M = Al, Ga, In) The courses of the ammonolysis reactions of the ammonium hexafluorometalates (NH₄)₃MF₆ (M = Al, Ga, In) were investigated with the aid of in‐situ powder diffractometry and differential thermal analysis. Under these conditions, the reaction of (NH₄)₃AlF₆ with gaseous ammonia yields at about 360 °C AlF₃ via the intermediates NH₄AlF₄, Al(NH₃)₂F₃ and Al(NH₃)F₃. The ammonolysis of (NH₄)₃GaF₆ produces GaN at about 400 °C. Depending upon the actual reaction conditions, the intermediates NH₄GaF₄ and Ga(NH₃)F₃ as well as their ammonia adducts NH₄GaF₄ · NH₃ and Ga(NH₃)₂F₃ and the amide‐ammoniate Ga(NH₃)(NH₂)F₂ are observed. In the case of (NH₄)₃InF₆ the intermediates (NH₄)₃InF₆ · NH₃ and In(NH₃)F₃ may exist; there are also indications for the reduction of In(III) to In(I) and for the existence of In(NH₃)₂F and InF as products of the ammonolysis of (NH₄)₃InF₆.     

Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

Homoallyl-Substituted Vinylcyclopropanes from α,β-Unsaturated Ketones and Allylindium Derivatives

Simply reversing the order of addition of aqueous acid and Et₂O to the Barbier intermediate 1 of the known indium-mediated allylation leads to unprecedented deoxygenative rearrangements [Eq. (a)].     

Sesquialkoxide von Gallium und Indium

Sesquialkoxides of Gallium and Indium Treatment of GaMe₃ with one equivalent of HO^cHex in toluene at 20 °C leads to [Me₂GaO^cHex]₂ ( 4 ) under evolution of methane. The reaction of InMe₃ with two equivalents of HO^cHex leads under similar conditions not to [MeIn(O^cHex)₂]_n but to the sesquialkoxide [In{Me₂In(O^cHex)₂}₃] ( 5 ). 5 can be described also as [{Me₂InO^cHex)}₂{MeIn(O^cHex)₂}₂]. The use of an excess of cyclohexanol in boiling toluene gives the same result. Under these reflux conditions, the reaction of GaMe₃ with an excess of PhCH₂OH leads exclusively to another type of sequialkoxides, [Ga{MeGa(OCH₂Ph)₃}₃] ( 6 ). 4 — 6 were characterized by NMR, vibrational and MS spectra, as well as by X‐ray structure determinations. According to this, 4 forms centrosymmetrical and therefore planar Ga₂O₂ four‐membered rings. 5 and 6 possess basically the same structural motif, central M³⁺ ion ( 5 : In³⁺; 6 : Ga³⁺) coordinated by three metalate units ( 5 : [Me₂In(O^cHex)₂]^—; 6 : [MeGa(OCH₂Ph)₃]^—). The central M³⁺ ions have always coordination number (CN) six while the three surrounding metal ions possess CN 4. Because of the spectroscopic findings 6 must exist in two isomers (1:1). The C₃‐symmetrical isomer C₃‐ 6 was characterized by X‐ray analysis, while the isomer C₁‐ 6 could by described mainly by the complex NMR data.