Base-freie Tris(trimethylsilyl)methyl-Derivate des Lithiums,Aluminiums, Galliums und Indiums

Base-free Tris(trimethylsilyl)methyl Derivatives of Lithium, Aluminium, Gallium, and Indium Base-free LiR* (R*=-C(SiMe₃)₃) has been prepared from R*Cl and Li-metal in toluene at 85?90°C and used to synthesize the metallanes R*MMe₂ with M = Al, Ga and In, respectively. The NMR (¹H, ¹³C, ²⁹Si) and the vibrational spectra of these trisyl compounds have been discussed. AlCl₃ and LiR*(ratio 1 : 1) forms the metallate metallate Li[R*AlCl₃]. The triclinic unit cell (space group P1 ) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl₃]- units with Al? Cl…?Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R₁wR₂ =0,0444/0,1072). The reaction of GaCl₃ with LiR* (I :1) gives the unusual sesquichloride (R*Ga(Cl_1,33)Me_0,67)₃ in moderate yield. The X-ray structure determination shows a Ga₃Cl₃-skeleton with chairconformation and disordered, terminal gallium ligands (R₁/wR₂= 0,0646/0,2270).     

Vinamidin-Chelate des Aluminiums und Galliums

Vinamidine Chelates of Aluminium and Gallium The vinamidine aluminum and gallium complexes C₅H₇R₂AlCl₂N₂ ( 8 ) and C₅H₇R₂Cl₂GaN₂ ( 9 ) (R = Me, ⁱPr, ^tBu) are obtained from the corresponding vinamidines and ECl₃ (E = Al, Ga) in moderate yields. Crystal structure analyses of 8 a , 8 b , 9 a and 9 c reveal a minor influence of the alkyl subtituents on the structure of the six membered rings. Ab initio calculations demonstrate polar Al–N and Ga–N bonds without significant π-interaction. The calculated ¹³C- and ²⁷Al-NMR shifts are reported.     

Neue Aminometallane des Aluminiums und Galliums

New Aminometalanes of Aluminum and Gallium The reaction of secondary amines R′RNH with trimethyaluminum leads to the formation of dimeric aminoalanes [RR′NAlMe₂]₂ ( 1 ) (R = 2,6-Me₂C₆H₃, R′ = SiMe₂(2,4,6-Me₃C₆H₂)) and 2 (R = Ph, R′ = SiMe₃). Using a different stoichiometric ratio, a monomeric aminoalane [RR′N]₂AlMe ( 3 ) (R = Ph, R′ = SiPh₂Me) is obtained, having an aluminum atom of coordination number three due to the steric demand of the substituents. The synthesis of the corresponding aminogallanes 4 , 5 and 6 is achieved by reaction of lithium amides LiNRR′ (R = Ph, 2,6-iPr₂C₆H₃; R′ = SiMe₃, SiMe₂iPr) with dimethylgalliumchloride, Me₂GaCl, in n-hexane. The formation of the dimeric species is in 1 through carbon while that in 2 and 3 is formed through nitrogen. The X-ray single crystal structure analysis of 1 , 2 , 3 and 4 are reported.     

Reaktionen einiger Methylmetallhalogenide des Aluminiums,Galliums und Indiums mit Hexamethyldisilazan

Reactions of some Methylmetal Halides of Aluminium, Gallium, and Indium with Hexamethyldisilazane MeAlCl₂ or MeGaBr₂, and bis(trimethylsilyl)amine form the dimeric, mixed-substituted ring molecules (Me(Hal)M^III–N(H)SiMe₃)₂ and one equivalent Me₃SiHal. The NMR (¹H, ¹³C, ²⁹Si) and vibrational spectra (IR, Raman) are measured and the X-ray structure analysis of the compound with M^III = Al and Hal = Cl, has been done as well. Me₂AlCl with an excess of HN(SiMe₃)₂ forms the expected amide (Me₂Al–N(H)SiMe₃)₂, the homologue Me₂GaCl with HMDS, however, gives at 50–55 °C only the cyclic (1 : 1) adduct (Me₂Ga–N(H)SiMe₃) · (Me₂GaCl). This complex crystallizes in the space group Cmc2₁, the unit cell consists of four binucleate molecules with folded Ga–N–Ga–Cl-ring skeletons.     

Neubestimmung von Struktur und Eigenschaften isotyper Natriumtetraamidometallate des Aluminiums und Galliums

Redetermination of Structure and Properties of the Isotypic Sodium Tetraamido Metallates of Aluminium and Gallium Crystals for x-ray structure determination of NaAl(NH₂)₄ and NaGa(NH₂)₄ were obtained by the reaction of the metals with ammonia in autoclaves at 100°C and P(NH₃) = 60 bar within 7 days. The compounds crystallize isotypic in the space group P2₁/c with Z = 4 NaAl(NH₂)₄ a = 7.328(2) Å, b = 6.047(2) Å, c = 13.151(3) Å, β = 94.04(1)° NaGa(NH₂)₄ a = 7.4087(8) Å, b = 6.0917(5) Å, c = 12.855(2) Å, β = 92.10(1)° The structures were refined inclusively all H-positions of the amide ions. The ternay amides are furthermore characterized by their IR spectra and their thermal behaviour.     

Darstellung,Eigenschaften und Molekülstrukturen von Dimethylmetallalkoxiden und ‐amiden des Aluminiums und Galliums

Preparation, Properties, and Molecular Structures of Dimethylmetal Alkoxides and Amides of Aluminium and Gallium Dimethylaluminium‐ ( 1 ) and Dimethylgallium‐o‐methoxyphenyl‐1‐ethoxide ( 2 ) were obtained by reaction of Me₃Al and Me₃Ga respectively with o‐Methoxyphenyl‐1‐ethanol in n‐pentane. Dimethylaluminium‐ ( 3 ) and dimethylgallium‐o‐methoxyphenyl‐2‐ethylamide ( 4 ) were prepared by treatment of Me₂AlCl and Me₂GaCl respectively with Lithium‐o‐methoxyphenyl‐2‐ethylamide. Trimethylgallium‐o‐methoxyphenylmethylamine‐Adduct ( 5 ) was isolated using reaction of Me₃Ga with the corresponding amine. The compounds were characterised by ¹H‐, ¹³C‐, and ²⁷Al n.m.r. spectroscopy. The molecular structures of 2 and 5 were determined by X‐ray diffraction. Compounds 1 – 4 form brigded dimeric molecules. The bond distances of the central Ga₂O₂ ring in 2 correspond to those of compounds of similar structure.     

Nachweis und Bestimmung des Aluminiums

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Nachweis und Bestimmung des Aluminiums

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Nachweis und Bestimmung des Aluminiums

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Die Nitrate des Chroms und Aluminiums

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Zur Trennung des Aluminiums und Zirkoniums

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Zur Scheidung und Bestimmung des Arsens

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Zur Bestimmung und Trennung des Arsens,Antimons und Zinns

Analytical and Bioanalytical Chemistry -     

Ternäre Bromide des Aluminiums,Galliums und Indiums vom Typ AIMIIIBr4 (AI = Na,Ga, K,In, Rb) Eine Übersicht

Ternary Bromides of Aluminium, Gallium, and Indium of the Formula Type A^IM^IIIBr₄ (A^I = Na, Ga, K, In, Rb). An Overview The fourteen possible bromides A^IM^IIIBr₄ with A^I = Na, Ga, K, In, Rb and M^III = Al, Ga, In are obtained from mixtures of the binary components, ABr and MBr₃. Six different structure types are observed: NaGaBr₄-, NaAlCl₄-, GaCl₂-, β-GaBr₂-, KAlBr₄-, and BaSO₄-type. Singlecrystal data are reported for the examples of NaGaBr₄, KGaBr₄, and InGaBr₄. Without exception, slightly distorted tetrahedra [MBr₄]^? occur. The structural variety must be sought in the adjustment of the coordinational needs of the counter cations A⁺ (coordination numbers between six and twelve).     

Zur Reaktion von cyclo‐Tristannazanen, [(CH3)2Sn–N(R)]3, mit den Trimethylderivaten des Aluminiums,Galliums und Indiums

The Reactions of cyclo ‐Tristannazanes, [(CH₃)₂Sn–N(R)]₃, with the Trimethyl Derivatives of Aluminium, Gallium, and Indium The cyclo‐tristannazanes [Me₂Sn–N(R)]₃ (with R = Me, ⁿPr, ⁱPr, ⁱBu) have been prepared from Me₂SnCl₂ and LiN(H)R in a 1 : 2 molar ratio. With MMe₃ (M = Al, Ga, In) they form the dimeric dimethylmetal trimethylstannyl(alkyl)amides [Me₂M–N(R)SnMe₃]₂ in good yields. The mass, NMR (¹H, ¹³C, ¹¹⁹Sn), and vibrational spectra are discussed and compared with the spectra of the tristannazanes. Thermolysis of the gallium amidocompounds splits SnMe₄ to form methylgallium imido derivatives with cage structures. The crystal structures of selected stannylamido complexes have been determined by X‐ray structure analysis.     

Die Abtrennung des Vanadiums und Scandiums von Titan bzw. des Arsens von Germanium (und Gallium)

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Zur Analyse des Aluminiums und seiner Legierungen

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Zur Bestimmung und zur Trennung des Aluminiums

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Ueber einige Trennungs- und Bestimmungsmethoden des Arsens, Antimons und Zinns

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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.