Reductive elimination: a pathway to low-valent aluminium species

Ganesamoorthy, Chelladurai; Loerke, Sinah; Gemel, Christian; Jerabek, Paul; Winter, Manuela; Frenking, Gernot; Fischer, Roland A.

doi:10.1039/c3cc38584a

Cited by 96 publications

(74 citation statements)

References 42 publications

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“…The reduction of [Cp*AlCl 2 ] with potassium, or of [Cp*AlX 2 ] (X=Cl, Br, I) with Na/K alloy, was found to provide B (Figure (ii)), whereas, alternatively, Ganesamoorthy et al. discovered that [Cp* 2 AlH] undergoes reductive elimination of Cp*H upon heating, leading to B (Figure (iii)) …”

Section: Introductionmentioning

confidence: 99%

Lewis‐Base‐Induced Disproportionation of a Dialane

Hofmann

Lamprecht

Jiménez‐Halla

et al. 2018

Chemistry A European J

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Section: Introductionmentioning

confidence: 99%

Lewis‐Base‐Induced Disproportionation of a Dialane

Hofmann

Lamprecht

Jiménez‐Halla

et al. 2018

Chemistry A European J

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“…1,[13][14][15] Aluminium hydrides are considered as fuel storagematerials with reasonable prospects in a hydrogen-based alternate energy-supply concept. 16,17 Moreover, the application of aluminium hydrides in the synthesis of low-valent aluminium compounds has been reported and III 18 ( Fig. 1) is a very recent example among others 19 of an intriguing nature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and reactivity of an imidazolin-2-iminato aluminium dihydride

2014

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The reaction of bis(2,6-diisopropylphenyl)imidazolin-2-imine (LH, 1) with Me 3 N·AlH 3 furnishes {μ-LAlH 2 } 2 (2). The marked tendency of 2 to release its hydride substituents is ascribed to the strong electron-donor character of the imidazolin-2-iminato ligand. This is supported by its reactivity study and DFT calculations.In fact, compound 2 was further converted with Me 3 SiOTf, Me 2 S·BH 3 , Me 2 S·BBr 3 , and BX 3 (with X = Cl, Br, and I) into {μ-LAl(H)OTf} 2 (3), {μ-LAl(BH 4 ) 2 } 2 (4), and {μ-LAlX 2 } 2 (5, X = Br; 6, X = Cl; 7, X = I), respectively.For all new aluminium complexes the formulation as dimers was evidenced by high resolution mass spectrometry, as well as single-crystal X-ray diffraction analysis. A prominent structural motif of these compounds is the square-planar four-membered Al 2 N 2 ring with two bridging bulky imidazolin-2-imino moieties. IntroductionAluminium hydrides -versatile reagents with rich chemistry For many years, chemical synthesis has been gaining immense benefit from the distinct reactivity of the aluminium-hydrogen bond. The strong need for highly selective transformations, increased focus on safety considerations, and efficiency in handling and storage are only some reasons why we find the chemically rogue parent aluminium hydride tamed into more suitable forms today. A variety of hydridoalanes has been tailored and very often reactivity adjustment is realized by steric congestion at the aluminium centre and by attaching strongly electron-donating substituents to the aluminium atom. Furthermore, hydridoalanes are used in a diverse range of applications. For instance, the hydroalumination of carbonyl 1,2 and alkyne 3-7 functionalities is a common application for this class of compounds in organic synthesis. Though the intermediate aluminium species in these reactions are often elusive, the use of aluminium hydrides such as I 8 ( Fig. 1) that bear highly sophisticated ligands grants access to all types of isolatable and well-defined model complexes. Compound I can be categorized as an aluminium dihydride and is related to the parent aluminium trihydride by replacement of one hydride for an anionic ligand. Thus, an ancillary ligand may be introduced, and yet, two reactive functional groups at the metal centre are preserved for the purpose of follow-up chemistry. The β-diketimino group, in particular, has been a key ligand to a rich chemistry of respective aluminium dihydrides. 9-12 A prominent example is II (Fig. 1), which can View Article OnlineView Journal | View Issue be used for the activation of non-polar element-element bonds as demonstrated by its conversion with elemental sulphur or selenium. 9,10 In a different field of applied science one finds chemical vapour deposition technology exploiting the thermodynamic properties of molecular aluminium hydrides for the purpose of creating composite materials. 1,13-15Aluminium hydrides are considered as fuel storagematerials with reasonable prospects in a hydrogen-based alternate energy-supply concept. 16,17 Moreover, the...

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“…The NMR spectroscopic data for 3 were also observed. Hence, DMAP did not react with the unknown aluminum compound, whereas the formation of 3 is likely due to a reaction of [Al{OSi(OtBu) 3 26). No signal in the 1 H NMR spectrum could be detected for the ammonium protons or OH group in 4 or 5.…”

Section: Resultsmentioning

confidence: 91%

“…[Cp*Al] 4 [26] (1) and iPr 2 Si(OH)(μ-O)Si(OH)iPr 2 [27] were prepared according to literature procedure. Deionized water was degassed three times by freeze-pump-thaw procedure.…”

Section: Methodsmentioning

confidence: 99%

Reactivity of Cp*Al towards Silanols: Formation and Hydrolysis of Alumosiloxanes

2018

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Reductive elimination: a pathway to low-valent aluminium species

Abstract: Compounds CpAlH2 (1) and Cp2AlH (2) reductively eliminate CpH in benzene or toluene under reflux conditions to give Al(s) and AlCp, respectively.

Cited by 96 publications

References 42 publications

Lewis‐Base‐Induced Disproportionation of a Dialane

Lewis‐Base‐Induced Disproportionation of a Dialane

Synthesis, characterization and reactivity of an imidazolin-2-iminato aluminium dihydride

Reactivity of Cp*Al towards Silanols: Formation and Hydrolysis of Alumosiloxanes

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Reductive elimination: a pathway to low-valent aluminium species

Abstract: Compounds Cp*AlH2 (1) and Cp*2AlH (2) reductively eliminate Cp*H in benzene or toluene under reflux conditions to give Al(s) and AlCp*, respectively.

Cited by 96 publications

References 42 publications

Lewis‐Base‐Induced Disproportionation of a Dialane

Lewis‐Base‐Induced Disproportionation of a Dialane

Synthesis, characterization and reactivity of an imidazolin-2-iminato aluminium dihydride

Reactivity of Cp*Al towards Silanols: Formation and Hydrolysis of Alumosiloxanes

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Abstract: Compounds CpAlH2 (1) and Cp2AlH (2) reductively eliminate CpH in benzene or toluene under reflux conditions to give Al(s) and AlCp, respectively.