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.     

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.     

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.     

Methylmetall-bis(trimethylsilyl)amidoderivate des Aluminiums,Galliums und Arsens

Methyl Metal Bis(trimethylsilyl)amido Derivatives of Aluminium, Gallium, and Arsenic MeAl[N(SiMe₃)₂]₂ (Me ? CH₃) has been prepared by the reaction of AlMe₃ with HN(SiMe₃)₂ in a 1:2 molar ratio. The homologue Gallium compound (as well as the Aluminium derivative) is formed in good yields by the interaction of MeMcl₂ (M = Al, Ga) with Li- and Na[N(SiMe₃)₂], respectively. MeAs[N(SiMe₃)₂]₂ is formed by the reaction of AsCl₃ and Na[N(SiMe₃)₂] in a 1:3 molar ratio. These colourless amido derivatives are monomeric in solution, they have been characterized by analyses, mass, n.m.r. (¹H and ¹³C), and especially by i.r. and Raman spectra.     

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).     

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.     

Neue Alkalimetallchromchalkogenide und ihre Struktursystematik

New Alkali Metal Chromium Chalcogenides and their Structural Classification The compounds RbCr₃S₅, K₃Cr₁₁S₁₈, RbCr₅Se₈ and CsCr₅Se₈ could be obtained in the form of wellshaped crystals via fusion reactions of the alkali metal carbonates with chromium and the corresponding chalcogen. The compounds crystallize in the monoclinic space groups C2/m (RbCr₃S₅: a = 19.372(3) Å, b = 3.498(1) Å, c = 12.119(2) Å, β = 122.78(1)°, Z = 4; K₃Cr₁₁S₁₈: a = 41.876(3) Å, b = 3.463(1) Å, c = 16.315(3) Å, β = 150.07(1)°, Z = 2; RbCr₅Se₈: a = 18.737(2) Å, b = 3.623(1) Å; c = 9.016(1) Å, β = 104.65(1)°, Z = 2; CsCr₅Se₈: a = 18.795(2) Å, b = 3.637(1) Å, c = 9.104(1) Å, β = 104.52(1)°, Z = 2). We propose a structure classification from group-subgroup-relations. MAPLE calculations reveal that the reactions of the binary chalcogenides to yield the ternary compounds are exothermic in each case and are dependent on the chromium/alkali metal ratio in the ternary chalcogenides.     

Neue ternäre Phosphide und Arsenide des Caesiums mit Elementen der 8. Nebengruppe

New Ternary Phosphides and Arsenides of Cesium and Element of the 8th Transition Metal Group In the ternary systems Cesium/8^th transition metal group/5^th main group some new compounds were found and investigated. By single crystal measurements CsRh₂P₂ was found to crystallize in the space group 14/mmm with the lattice constants a = 390.11 pm and c = 1429.36 pm. The new compounds with the formula CsM₂X₂ (M = Fe, Co, Ru, Rh, Ir; X = P or As) crystallize in the ThCr₂Si₂-type structure, compounds of the formula Cs₂MX₂ (M = Ni, Pd, Pt; X = P or As) can be placed in a line with the K₂PdP₂-type 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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Neue ternäre Verbindungen des Caesiums mit Elementen der 8. Nebengruppe und 5. Hauptgruppe

New Ternary Compounds of Cesium and Elements of the 8^th Transition Metal Group and the 5^th Main Group In the ternary systems Cesium/element of the 8^th transition metal group/element of the 5^th main group some new compounds were found and investigated. Compounds of the formula Cs₂MX₂ (M = Pt, Pd, Ni; X = P, Sb, Bi) can be placed in a line with the K₂PdP₂-type structure. The new compound with the formula CsFe₂Sb₂ crystallizes in the ThCr₂Si₂-type structure. By single crystal measurements CsFe₂As₂ was found to crystallize in the space group I4/mmm with the lattice constants a = 389.43 pm and c = 1 509.97 pm.     

Die Nitrate des Chroms und Aluminiums

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Zur Trennung des Aluminiums und Zirkoniums

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Zur Bestimmung und zur Trennung des Aluminiums

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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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Synthese und strukturelle Studien von Aluminiumdialkylaminen und ‐amiden: N‐Chiralität von (CH3)3AlNHRR′ und cis‐trans‐Isomerie an X2AlNRR′ (X = CH3, Cl,H)

Synthesis and Structural Studies of Aluminum Dialkylamines and Dialkylamides: N‐Chirality of (CH₃)₃AlNHRR′ and cis‐trans ‐Isomerism at X₂AlNRR′ (X = CH₃, Cl, H) Aluminum dialkylamines and dialkylamides were prepared from Al(CH₃)₃ and NH(CH₃)R′ (R′: –C₂H₅, –^tC₄H₉) and characterized by elemental analyses, ¹H‐, ¹³C‐, and ²⁷Al‐NMR spectroscopy. The crystal structures of [(CH₃)₂AlN(CH₃)(–^tC₄H₉)]₂ ( IV ), [Cl₂AlN(CH₃)(C₂H₅)]₂ ( V ), and [H₂AlN(CH₃)(C₂H₅)]_∞ ( VI‐trans and VI‐cis ) are discussed.