Stabilisierung von M+‐Ionen (M = In,Tl) durch Dibenzyldichlorogallat

Stabilization of M⁺ Ions (M = In, Tl) by Dibenzyldichlorogallate MCl reacts with (PhCH₂)₂GaCl to give M[(PhCH₂)₂GaCl₂] [M = In ( 1 ), Tl ( 2 )]. 1 and 2 were characterized by NMR, IR and MS techniques. In addition, an X‐ray structure determination of 1 was performed. According to this, 1 consists of four‐membered In₂Cl₂ rings connected by weak In…Cl contacts (344 pm) along [010] to a coordination polymer. The In⁺ ion is coordinated by four In–Cl and two In‐aryl interactions.     

M2Ga6Te10 (M: Li,Na): Two New Non‐metallic Filled β‐Manganese Phases – X‐ray and NMR Studies

Two new non‐metallic filled β‐manganese phases M₂Ga₆Te₁₀ (M: Li, Na) are obtained as black, homogeneous, microcristalline samples as well as single crystals by direct reaction of the elements. According to the single crystal structure determinations both compounds crystallize in space group R32 (No. 155, Z = 2) with the lattice constants: a = 1436.9(2), c = 1759.0(4) pm (T = 180 K, Li₂Ga₆Te₁₀) and a = 1458(1) pm, c = 1776.1(4) pm (T = 290 K, Na₂Ga₆Te₁₀). Their structures are characterized by tetrahedral close packings of Te^2–, corresponding to the arrangement of Mn atoms in β‐Mn. While Ga³⁺ ions are distributed in an ordered way over 12% of the tetrahedral holes, the M⁺ ions occupy all distorted octahedral (“metaprismatic”) holes. As the Li⁺ ions are too small they occupy off‐center positions inside the metaprisms. Positions with the strongest off‐centering can only be refined on the basis of a split model. MAS‐NMR measurements, including multiple quantum NMR, allowed the two different crystallographic M⁺ sites to be distinguished unambigously by separate ⁷Li and ²³Na signals, respectively. The assignment of the NMR signals was supported by measurements of samples in which Li⁺ was partly substituted by larger cations (Sn²⁺, Pb²⁺).     

Darstellung,Eigenschaften und Molekülstrukturen von Dimethylaminomethylferrocenyl‐Verbindungen ausgewählter Elemente der Gruppen 13 und 14

Preparation, Properties, and Molecular Structures of Dimethylaminomethyl Ferrocenyl Compounds of selected Elements of Group 13 and 14 Dimethylmetalchlorides of gallium and indium react with dimethylaminomethylferrocenyllithium (FcNLi) to give the corresponding dimethylmetaldimethylaminomethylferrocenes 1 and 2 [Me₂MFcN; M=Ga, In]. In a similar manner dialkylmetaldichlorides of germanium and tin yield the expected chlordialkylmetaldimethylaminomethylferrocenes 3 – 5 [R₂(Cl)MFcN; M=Ge; R = Me ( 3 ), M=Sn; R=Me ( 4 ), Ph ( 5 )]. In a reaction of Me₃Al and Me₂AlCl with dimethylaminomethylferrocene the formation of the 1 : 1 adducts 7 and 8 could be observed. All compounds were characterised by ¹H and ¹³C nmr spectroscopy. The molecular structures of 1 , 3 , 4 and 7 were determined. 3 and 4 build in contrast to 1 monomeric molecules with chelat rings as a result of the M–N coordination. Compound 7 consist of monomeric molecules with 4 coordinated Al atoms.     

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.     

吸附于纳米磷化镓粉体表面碱性品红的拉曼光谱(英文)

本文中,对吸附于纳米磷化镓(GaP)粉体表面的碱性品红拉曼光谱进行了研究。通过将吸附碱性品红与纯碱性品红晶体样品的拉曼光谱进行对比、分析可知,碱性品红在纳米GaP粉体表面发生了化学吸附。在吸附碱性品红样品的拉曼光谱中,位于1200~1320cm-1范围内的光谱特征表明可能有新的化学键(P-O-C+或Ga-O-C+)形成。碱性品红分子的中央碳正离子(C+)与GaP表面具有孤对电子的氧原子形成配位键。红外光谱结果表明,氧原子与纳米GaP粉体表面的磷原子或镓原子键合,以P-O,Ga-O或P-O-Ga形式存在于GaP表面。碱性品红分子的呼吸振动,N-苯环伸缩振动,以及苯环C-C伸缩振动散射强度与纯碱性品红晶体样品相比皆有所增强。N-苯环伸缩振动散射强度增加意味着N原子是除C+离子以外的另一个可以与GaP表面发生化学作用的活性中心,这种化学作用是由N原子与GaP表面存在共轭效应造成的。     

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.     

A Silatetragallane—Classical Heterobicyclopentane or closo-Polyhedron?

Classical and nonclassical can be used to describe the bonding in the polyhedral Ga₄Si framework of the silagallanate ion [Me₃SiSi{GaSi(SiMe₃)₃}₃GaSiMe₃]⁻ (the GaSi framework is depicted in the picture). This is the result of density functional calculations that were carried out on model compounds. The cluster was obtained by ultrasonication of gallium and iodine and subsequent reaction with (Me₃Si)₃Li(thf)₃.     

Über den Einfluß von Substitution auf die Kristallstruktur von SrNi2P2

About the Effect of Substitution on the Crystal Structure of SrNi₂P₂ With several series of mixed crystals the effect of substitution on the crystal structure of SrNi₂P₂ (polymorphic, the structures are variants of the ThCr₂Si₂ type) is investigated by X-ray methods. In the compound Ni completely can be substituted by Co and Cu respectively and also P by As; in Sr_1–xCa_xNi₂P₂ there is a gap of the miscibility between 0.3 ≤ x ≤ 0.6. A low substitution of the several elements more than proportionally changes the structure parameters. In this range the mixed crystals with Ca, Cu, and As, respectively, undergo first order phase transitions with significant changes of the bond distances, which will be interpreted by the results of band structure calculations.     

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.     

Chemischer Transport fester Lösungen. 11 [1] Mischphasen und Chemischer Transport in den Systemen CrIII/InIII/GeIV/O,GaIII/InIII/GeIV/O,MnIII/InIII/GeIV/O und FeIII/InIII/GeIV/O

Chemical Vapor Transport of Solid Solutions. 11 Mixed Phases and Chemical Vapor Transport in the Systems Cr^III/In^III/Ge^IV/O, Ga^III/In^III/Ge^IV/O, Mn^III/In^III/Ge^IV/O und Fe^III/In^III/Ge^IV/O By means of chemical vapor transport methods the following mixed phases have been prepared: Cr_{0, 18}In_{1, 82}Ge₂O₇ (Cl₂, 950 → 850 °C), (Ga_{0, 6}In_{1, 4})₂Ge₂O₇ (Thortveitit‐type, Cl₂, 1050 → 950 °C), (Ga_{1, 9}In_{0, 1})₂Ge₂O₇ (Ga₂Ge₂O₇‐type, 1050 → 950 °C), (In_{1, 9}Mn_{0, 1})₂Ge₂O₇ (Thortveiti‐type, Cl₂, 1000 → 800 °C), mixed phase crystallizing in the Mn₂Ge₂O₇‐structure showing a composition near MnInGe₂O₇ (Cl₂, 1000 → 800 °C), Mn_{6, 5}In_{0, 5}GeO₁₂ (Braunit‐type, Cl₂, 1000 → 800 °C), (Fe_xIn_1‐x)Ge₂O₇ (Thortveitit‐type with x = 0…0, 94; Cl₂, 840 → 780 °C). Changing the compositions of the starting materials showed no effect on the composition of the deposit except for the system Fe₂O₃‐In₂O₃‐GeO₂.