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67849108259
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In the same way, our investigations on the preparation of Al/Ga clusters5 via high-temperature molecules like AlCl were initiated by our former matrix-isolation and spectroscopy experiments on the reactivity of species like AlCl and SiO.6-8
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67849115943
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Ongoing experimental and theoretical investigations will be subject of a separate publication
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Ongoing experimental and theoretical investigations will be subject of a separate publication.
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84869564824
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Crystallographic data and refinement parameters for 2: empirical formula, C48H108Al4P6; fw, 979.08; T, 150(2) K; λ, 0.71073 Å; cryst syst, monoclinic; space group, P21/c; a, 21.1040(14) Å, b, 12.4808(8) Å, c, 23.3842(15) Å, β, 96.406(5)°; V, 6120.8(7) Å3; Z, 4; Dcalcd, 1.062 Mg/m 3; abs coeff, 0.261 mm-1; F(000, 2152; cryst size, 0.09 × 0.32 × 0.32 mm3; theta; range for data collection, 1.75 to 25.05°; index ranges, 25 ≤ h ≤ 25, 14 ≤ k ≤ 14,-27 ≤ l ≤ 27; reflns collected, 38587; independent reflns, 10760 (Rint, 0.0779, refinement method, full-matrix least-squares on F2; data/restraints/params, 10760/0/554; GOF on F2, 0.827; R1 [I > 2σI
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34
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84869586939
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The weak reflection intensity during the X-ray experiments on 2b did not allow a proper structure determination. Therefore, only the following results are presented: space group, P1; a, 11.881 Å, b, 11.922 Å, c, 21.188 Å, α, 83.18°, β, 84.28°, γ, 82.14°; V, 2941.1 Å3; Z, 2
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3; Z = 2.
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84869586935
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+), and consequently, their HOMOs have positive energies.
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+), and consequently, their HOMOs have positive energies.
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48
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67849099078
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The formation of the model cluster Al4H4(PH 2)2 2c can also be described in an alternative way, in terms of PR2- ligands that in reality should be present in the reaction mixture starting from LiPTBu2. In a gedankenexperiment, we start with an Al4H42+ cation, in which six electrons form the cluster bonding. The reaction with two PR2- anions, each containing two lone pairs, generates two very low lying orbitals in which Al, P, Al and Al4P2 moieties are the prominent entities and two orbitals that are nonbonding, as in the above-mentioned description of 2c. Thus, in this model we also have 10 electrons for the cluster bonding and four only weakly bonding electrons within the Al, P, Al bridges
-
2 moieties are the prominent entities and two orbitals that are nonbonding, as in the above-mentioned description of 2c. Thus, in this model we also have 10 electrons for the cluster bonding and four only weakly bonding electrons within the Al - P - Al bridges.
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84869586937
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67849126616
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This is also valid for the calculated and experimentally detected 27Al NMR shifts of Al4R4′ R, C 5Me4H, calcd 87.2 ppm; exptl 81.9 ppm
-
4H) (calcd 87.2 ppm; exptl 81.9 ppm).
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With respect to the partially neutralized species containing alkaline cations e.g, Al4Li
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Of the large number of publications in this field, see these two selections, which contain references to many other contributions: (a) Corbett, J. D. Angew. Chem., Int. Ed. 2000, 39, 692.
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