Donorstabilisiertes Aluminium(<scp>I</scp>)‐bromid

Mocker, M.; Robl, Christian; Schnöckel, Hansgeorg

doi:10.1002/ange.19941061731

Cited by 48 publications

(15 citation statements)

References 19 publications

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“…When freshly sublimed [{AlCp*} 4 ]8 and freshly isolated [{AlBr⋅NEt 3 } 4 ] ( 4 )9 were heated in heptane, the pale yellow suspension slowly turned orange, an initially beige precipitate turned brown, and finally Al metal precipitated. From this reaction mixture an orange heptane extract was obtained, from which orange crystals of 1 precipitated.…”

Section: Average Distances (Min/max) [Pm] In 1 Andmentioning

confidence: 99%

Al₂₀${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X₁₀ (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral Al_nX_m Molecules?

2005

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Dedicated to Professor Peter Paetzold on the occasion of his 70th birthdayTwo subgroups of Al-metal clusters with a predominant number of metal-metal bonds are known: [1] "naked" metalatom clusters, which are produced from solid metal by laser ablation techniques, and metalloid clusters, which are formed in solution starting with Al I species and, for example, subsequent reduction. [2,3] Here we present Al 20 Cp * 8 Br 10 (1) and Al 20 Cp * 8 Cl 10 (2) (Cp* = pentamethylcyclopentadienyl), two compounds of molecular, partially substituted subhalides belonging to the second group, which at first glance seem related to the species Al 13 I x À [4] and Al 14 I x À [5] (x = 1-12), which were generated in mass-spectrometric experiments. In both sets of compounds the halogen atoms form direct bonds to the Al atoms of the icosahedral Al 12 cluster core. However, quantum-chemical calculations for "naked" anionic clusters, for example, the Al 13 I x À anion mentioned above, indicate that an additional Al atom is located in the center.The structures of 1 and 2 are furthermore closely related to those of the recently characterized Al 22 X 20 compounds (X = Cl, Br), for example, Al 22 Br 20 (3) [6] because their cluster

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Section: Average Distances (Min/max) [Pm] In 1 Andmentioning

confidence: 99%

Al₂₀${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X₁₀ (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral Al_nX_m Molecules?

2005

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“…[22][23][24][25][26] Although low-valence aluminum compounds such as AlH, AlX (X=F, Cl, Br, I), and Al 2 O are well known, they are stable only at high temperatures and low pressures. [27][28][29][30][31] The pentamethylcyclopentadienyl aluminum tetramer (Cp * 4 Al 4 , 55 Cp * =C 5 Me 5 ) was the first pure Al(I) compound found to be stable at room temperature [32] . In Cp * 4 Al 4 , the four aluminum atoms form a regular tetrahedron, each of which is coordinated to a Cp * ring.…”

Section: Introductionmentioning

confidence: 99%

Influences of the substituents on the M–M bonding in Cp₄Al₄ and Cp₂M₂X₂ (M = B, Al, Ga; Cp = C₅H₅, X = halogen)

Sun

et al. 2015

Dalton Trans.

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Although the geometries of CpAl4 (Cp* = C5Me5) and Cp4Al4 (Cp = C5H5) are similar, CpAl4 is more stable than Cp4Al4. CpAl2I2 is the first complex involving an Al(ii)-Al(ii) bond to be supported by Cp-type ligands. In this work, the stability of CpAl4 and Cp4Al4 (Cp = C5H5), the nature of M-M bonding in Cp2M2X2 (M = B, Al, and Ga), and the influences of the X atom on the M-M bonds have been analyzed and compared within the framework of the atoms in molecules (AIM) theory, electron localization function (ELF), energy decomposition analysis (EDA), and natural bond orbital (NBO) analysis. The calculated results show that CpAl4 is more stable than Cp4Al4 because of HH interactions between the methyl groups on the same and different Cp rings and not because of the Al-Al bonds. In Cp2M2X2, the B-B bond is stronger than the Al-Al and Ga-Ga bonds. The B-B bond is most consistent with covalent bonding, whereas the Al-Al and Ga-Ga bonds are more consistent with metallic bonding. The strengths of the B-B bond increase in the sequence X = F, Cl, Br, and I, whereas the Al-Al and Ga-Ga bonds decrease in the sequence X = F, Cl, Br, and I. The different change tendencies arise from the different M-M bonds and the orbital interactions between atoms X and M.

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“…Behavior analogous to the disproportionation of 1 via a barrier may be valid for the subhalides AlX and Al 4 X 4 ·4L (X = Br, L = donor molecule, e.g., NEt 3 ) [33][34][35] (see the Supporting Information). However, the observation of intermediates (Al 22 X 20 ) [13,36] with a central icosahedral Al 12 core has been the basis for the hypothesis of a second nonmetallic modification of Al, which is metastable with respect to metallic Al by about 30 kJ.…”

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confidence: 99%

Experimentally Based DFT Calculations on the Hindered Disproportionation of [Al₄Cp*₄]: Formation of Metalloid Clusters as Intermediates on the Way to Solid Al Prevents the Decomposition of a Textbook Molecule

Huber

Henke

Schnöckel

2009

Chemistry A European J

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Lipase was covalently attached to multiwalled carbon nanotubes (MWNTs). Structural changes of the lipase upon attachment onto MWNTs were analyzed through circular dichroism and FTIR spectroscopy. The conjugate was utilized for the resolution of a model compound (R,S)‐1‐phenyl ethanol, and the reaction medium was n‐heptane. The enzymatic resolutions were carried out at temperatures from 35 to 60°C. The results show that the lipase attached onto MWNTs has significantly affected the performance of the enzyme in terms of temperature dependence and resolution efficiency. The activity of MWNT–lipase was less temperature‐dependent compared with that of the native lipase. The resolution efficiency was much improved with MWNT–lipase. MWNT–lipase retained the selectivity of the native lipase for (R)‐1‐phenyl ethanol. The consecutive use of MWNT–lipase showed that MWNT–lipase had a good stability in the resolution of (R,S)‐1‐phenyl ethanol. © 2010 American Institute of Chemical Engineers AIChE J, 2010

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Donorstabilisiertes Aluminium(I)‐bromid

Abstract: ZUSCHRIFTEN 4 konnten nach dem gleichen Mechanismus inhibierend wirken, wobei das Stickstoffatom mit einer Carboxylatgruppe wechselwirkt. Offensichtlich wird diese Wechselwirkung durch geometrische Faktoren nicht so sehr begunstigt, wodurch 4 ein schlechter Inhibitor als 2 ist.

Cited by 48 publications

References 19 publications

Al₂₀${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X₁₀ (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral Al_nX_m Molecules?

Al₂₀${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X₁₀ (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral Al_nX_m Molecules?

Influences of the substituents on the M–M bonding in Cp₄Al₄ and Cp₂M₂X₂ (M = B, Al, Ga; Cp = C₅H₅, X = halogen)

Experimentally Based DFT Calculations on the Hindered Disproportionation of [Al₄Cp*₄]: Formation of Metalloid Clusters as Intermediates on the Way to Solid Al Prevents the Decomposition of a Textbook Molecule

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Donorstabilisiertes Aluminium(I)‐bromid

Abstract: ZUSCHRIFTEN 4 konnten nach dem gleichen Mechanismus inhibierend wirken, wobei das Stickstoffatom mit einer Carboxylatgruppe wechselwirkt. Offensichtlich wird diese Wechselwirkung durch geometrische Faktoren nicht so sehr begunstigt, wodurch 4 ein schlechter Inhibitor als 2 ist.

Cited by 48 publications

References 19 publications

Al20${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X10 (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral AlnXm Molecules?

Al20${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X10 (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral AlnXm Molecules?

Influences of the substituents on the M–M bonding in Cp4Al4 and Cp2M2X2 (M = B, Al, Ga; Cp = C5H5, X = halogen)

Experimentally Based DFT Calculations on the Hindered Disproportionation of [Al4Cp*4]: Formation of Metalloid Clusters as Intermediates on the Way to Solid Al Prevents the Decomposition of a Textbook Molecule

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Al₂₀${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X₁₀ (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral Al_nX_m Molecules?

Al₂₀${{\rm Cp}{{\ast \hfill \atop 8\hfill}}}$X₁₀ (X=Cl, Br): Snapshots of the Formation of Metalloid Clusters from Polyhedral Al_nX_m Molecules?

Influences of the substituents on the M–M bonding in Cp₄Al₄ and Cp₂M₂X₂ (M = B, Al, Ga; Cp = C₅H₅, X = halogen)

Experimentally Based DFT Calculations on the Hindered Disproportionation of [Al₄Cp*₄]: Formation of Metalloid Clusters as Intermediates on the Way to Solid Al Prevents the Decomposition of a Textbook Molecule