Synthesis of a stable adduct of dialane(4) (Al2H4) via hydrogenation of a magnesium(I) dimer

Bonyhady, Simon J.; Collis, David; Frenking, Gernot; Holzmann, Nicole; Jones, Cameron; Stasch, Andreas

doi:10.1038/nchem.762

Cited by 227 publications

(190 citation statements)

References 32 publications

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“…For this procedure we found few reports in the literature merely reporting on respective iodinations. 19,[67][68][69] These comprise only one example 68 in which an aluminium hydride bearing a monodentate N-donor ligand is subject to conversion with I 2 and, thus, is strongly related to our report of a non-chelatefashioned iminato system. Notably, a mixture of products is obtained in this report and we interpret this in terms of an endorsement of our halogenation approach with BX 3 as an alternative option to X 2 .…”

Section: 43mentioning

confidence: 99%

“…Yield: 0. 19 Synthesis of {μ-LAlCl 2 } 2 (6). A stirring suspension of freshly sublimed AlCl 3 (0.38 g, 2.8 mmol) in toluene (8 mL) was cooled to 0°C and treated dropwise with a solution of {LLi} 2 (8, 1.11 g, 1.4 mmol) in toluene (19 mL) over a period of 10 min.…”

Section: Synthesis Of {μ-Lal(h)otf} 2 (3)mentioning

confidence: 99%

“…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. Recently, scarce σ-alane complexes of transition metals (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, scarce σ-alane complexes of transition metals (e.g. Cr, Mo, W, Mn) implementing ligands such as IV 19 ( Fig. 1) have been described.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: 43mentioning

confidence: 99%

Section: Synthesis Of {μ-Lal(h)otf} 2 (3)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Recently, scarce σ-alane complexes of transition metals (e.g. Cr, Mo, W, Mn) implementing ligands such as IV 19 ( Fig. 1) have been described.…”

Section: Introductionmentioning

confidence: 99%

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

2014

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“…123 Here, examples of the title compounds will be presented. A comprehensive survey about the interesting subject of NHC adduct formation with trivalent group 13 compounds, [124][125][126][127][128] however, is beyond the scope of this review. The frustrated carbene-borane Lewis pair 170a·B(C 6 F 5 ) 3 formed the aNHC-borane adduct 172 129 which is more stable than the corresponding nNHC-borane adduct.…”

Section: Interconversions Of Normal Abnormal and Remote N-heterocycmentioning

confidence: 99%

Recent advances in neutral and anionic N-heterocyclic carbene – betaine interconversions. Synthesis, characterization, and applications

Schmidt¹,

Wiechmann²,

Freese³

2013

Arkivoc

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Some mesoionic compounds, i.e. five-membered representatives of the class of conjugated mesomeric betaines (CMB), are in equilibrium with their tautomeric normal N-heterocyclic carbenes (nNHC). In addition, anionic N-heterocyclic carbenes, generated by deprotonation of mesoionic compounds, have been described. The first examples of conversions of crossconjugated mesomeric betaines (CCMB), 6-oxopyrimidinium-4-olates, into normal Nheterocyclic carbenes have been reported as well. CCMB such as imidazolium-4-carboxylate and pyrazolium-4-carboxylate can decarboxylate to form abnormal (aNHC) or remote N-heterocyclic carbenes (rNHC). Most conversions of betaines into N-heterocyclic carbenes start from pseudocross-conjugated mesomeric betaines (PCCMB) which can be regarded as heterocumulene adducts of nNHC. Thus, decarboxylations of imidazolium-2-carboxylates, 1,2,4-triazole-3-carboxylates, pyrazolium-3-carboxylates or indazolium-3-carboxylates yield N-heterocyclic carbenes which have been used in catalysis, complex chemistry, heterocyclic synthesis, and organocatalysis.

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The Chemistry of Low‐Valent Organoaluminum Species

Wehmschulte

2016

Patai's Chemistry of Functional Groups

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During the past 25 plus years, room‐temperature stable aluminum(I) and (II) compounds have become available through standard organometallic techniques, and their reactivity has been explored in much detail. The chemistry of aluminum(I) compounds may be viewed as that of a very reactive carbene (singlet and triplet, depending on the substrate). Typical reactions involve insertions into various EE or EX bonds and adduct formation with Lewis acids. Aluminum(II) compounds are generally dialumenes (R2AlAlR2) featuring an AlAl single bond. Their chemistry is similar to that of alanes (R3Al) with respect to substitutions and Lewis acid base chemistry but with a strong redox component. In many cases, substrates insert into the AlAl bond in a formally oxidative manner.

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Synthesis of a stable adduct of dialane(4) (Al2H4) via hydrogenation of a magnesium(I) dimer

Cited by 227 publications

References 32 publications

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

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

Recent advances in neutral and anionic N-heterocyclic carbene – betaine interconversions. Synthesis, characterization, and applications

The Chemistry of Low‐Valent Organoaluminum Species

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