- HeI photoelectron spectroscopy of trialkylaluminum and dialkylaluminum hydride compounds and their oligomers
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The HeI photoelectron spectra of trimethylaluminum, triethylaluminum, dimethylaluminum, and diethylaluminum hydrides were recorded as a function of temperature. From the spectra observed at different temperatures the spectra of the pure monomers and the trimethylaluminum, dimethylaluminum, and diethylaluminum hydride dimers and some of the bands related to the dimethylaluminum hydride trimer have been obtained. The spectra were interpreted with the aid of ab initio quantum chemical calculations, including Hartree-Fock/Koopmans, outer valence Green's function, and equation of motion coupled-cluster ionization energy calculations. The vertical ionization energies predicted by the latter two methods are in excellent agreement with the experimental values. Furthermore, the association capability of these compounds, the effects of the substituents, and the degree of association on the electronic structure are also discussed.
- Vass, Gábor,Tarczay, Gy?rgy,Magyarfalvi, Gábor,B?di, András,Szepes, László
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- Aluminum Hydride Catalyzed Hydroboration of Alkynes
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An aluminum-catalyzed hydroboration of alkynes using either the commercially available aluminum hydride DIBAL-H or bench-stable Et3Al?DABCO as the catalyst and H-Bpin as both the boron reagent and stoichiometric hydride source has been developed. Mechanistic studies revealed a unique mode of reactivity in which the reaction is proposed to proceed through hydroalumination and σ-bond metathesis between the resultant alkenyl aluminum species and HBpin, which acts to drive turnover of the catalytic cycle.
- Bismuto, Alessandro,Thomas, Stephen P.,Cowley, Michael J.
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supporting information
p. 15356 - 15359
(2016/12/06)
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- Synthesis of trialkylaluminum derivatives by the reaction of non-solvated aluminum hydride with α-olefins
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Hydroalumination of α-olefins by non-solvated polymeric aluminum hydride (AlH3)n occurs at 120-140°C. Mechanochemical activation accelerates this reaction. The addition of catalytic amounts of the prepared R3Al forms to the reaction system decreases the temperature of the process to 90-100°C. The greatest initiation effect is observed when ate-complexes of the MAlR4 type (M = Li, Na) are used: the reaction occurs with a higher rate already at 60-90°C affording R3Al free of admixtures of carbalumination products and dimers of α-olefins.
- Gavrilenko
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p. 1161 - 1163
(2007/10/03)
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