Spectrofluorimetric Determination of Trace Amounts of Gallium with Salicylaldehyde Benzoylhydrazone

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丙烷在无机膜反应器中的芳构化

研究了在固定床反应器和膜反应器中的丙烷芳构化，考察了ＨＺＳＭ－５担载的Ｇａ和Ｐｔ－Ｇａ催化剂对反应的影响。结果表明，采用无机膜反应器可以提高丙烷芳构化选择性，从而提高芳烃收率达１０％以上。在膜反应器中，低碳烷烃选择性降低，烯烃选择性增强。固定床相比，膜反应器在低温时对芳构化反应的促进作用最为显著，但是随着温度升高，其促进作用减弱。     

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.     

Four‐ and Five‐Coordinate Gallium Complexes Stabilized by Bidentate 2‐(Dimethylaminomethyl)Pyrrole Ligand: Molecular Structures of Ga[NC4H3(CH2NMe2)‐2]3 and GaMe2[NC4H3(CH2NMe2)‐2]

Treatment of GaCl₃ with one equiv of Li[NC₄H₃(CH₂NMe₂)‐2] (n = 1, 2, 3) in diethyl ether at ?78 °C yields GaCl_3‐n[NC₄H₃(CH₂NMe₂)‐2]_n (n = 1, 1 ; n = 2, 2 ; n = 3, 3 ). Compound 1 reacts with two equiv of RLi to afford GaR₂[NC₄H₃(CH₂NMe₂)‐2] ( 4a, R=Me; 4b, R=Bu ) via transmetallation. Reacting 2 with one equiv of RLi in diethyl ether, 3 and 4 are formed via ligand redistribution. Variable temperature ¹H NMR spectroscopic experiments reveal that the five‐coordinate gallium compound 3 is fluxional and results in a coalescence temperature at 5 °C, at which ΔG^≠ is calculated at ca. 10.4 Kcal/mole. All the new compounds have been characterized by ¹H and ¹³C NMR spectroscopy and the structures of compounds 3 and 4a have also been determined by X‐ray crystallography.     

Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.     

A concise method for synthesis of diaryl aryl- or alkylphosphonates

A convenient method has been developed to synthesize diaryl arylphosphonates from triaryl phosphites, triethyl phosphite, and aromatic halides. The new method relies on the triethyl phosphite assisted nickel catalyzed Arbuzov reaction and can be applied to synthesize certain diaryl alkylphosphonates without catalysts.     

Novel gallium-mediated C3-allylation of indoles and pyrroles in aqueous media promoted by Bu4NBr

A mild and efficient protocol for the coupling of indoles and pyrroles with allyl halides such as allyl bromide, crotyl bromide and propargyl bromide in the presence of gallium metal in a Bu₄NBr-DMF-H₂O system has been developed. The reaction is equally effective when cadmium is used in lieu of gallium and the corresponding 3-allyl indoles and 3-allyl pyrroles were obtained in almost comparable yields.     

胡椒基荧光酮光度法测定粉煤灰中微量镓

在表面活性剂OP存在下,镓与胡椒基荧光酮(PIF)在pH 6.0 HAc-NaAc缓冲溶液中形成蓝紫色配合物,其表观摩尔吸光系数为8.51×104L.mol-1.cm-1,最大吸收波长为568 nm,配合物的组成比为n(Ga(Ⅲ))∶n(PIF)=1∶4。镓质量浓度在0~0.5μg/mL范围内符合比耳定律,镓(Ⅲ)的标准加入回收率在96.5%~102.1%之间。结合乙酸丁酯萃取分离干扰元素,用于测定粉煤灰中微量镓。