Tetrasupersilyldialuminum [(t-Bu)3Si]2Al−Al[Si(t-Bu)3]2:  The Dialane(4) with the Longest Al−Al Bond to Date,

Wibeŕg, Nils; Amelunxen, Kerstin; Blank, Thomas; Nöth, Heinrich; Knizek, Jörg

doi:10.1021/om980469r

Cited by 79 publications

(81 citation statements)

References 13 publications

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“…After removal of all volatile components in an oil pump vacuum, the residue was taken up in toluene (80 mL), the insoluble components (NaCl) were filtered, and the filtrate was concentrated to 20 mL, deep violet R* 4 In 2 (1.12 g, 1.09 mmol; 63 %) crystallized from the solution at À 23 8C. [5] R* 8 Si NMR spectra of the reaction solution, the diindane completely decomposed after replacement of C 6 D 6 for heptane, leading to supersilane tBu 3 SiH (identified by comparison with authentic sample [2] ) and an indiumand supersilyl-containing product (two different types of SitBu 3 groups in the ratio 1:1); 1 29 Si NMR: d 64.2 and 50.9). After removal of all volatile components in an oil pump vacuum, the residue was taken up in benzene (40 mL), and the solution was concentrated to 10 mL, R* 8 In 12 (0.05 g, 0.02 mmol; ca.…”

Section: Dedicated To Professor Helmut Werner On the Occasion Of His mentioning

confidence: 99%

Dodecaindane (tBu3Si)8In12—A Compound with an In12 Deltapolyhedron Framework

Wibeŕg¹,

Blank²,

Nöth³

et al. 1999

Angew. Chem. Int. Ed.

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A unique feature among polyhedron frameworks of boron group elements is exhibited by the In framework of the black-violet dodecaindane R In (R*=SitBu ), which can be obtained by the thermolysis of R In-InR . The molecular structure of R In (tBu groups omitted in picture shown) can be described as a combination of two R In octahedral building blocks and can thus be classified as a conjuncto dodecaindane.

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Section: Dedicated To Professor Helmut Werner On the Occasion Of His mentioning

confidence: 99%

Dodecaindane (tBu3Si)8In12—A Compound with an In12 Deltapolyhedron Framework

Wibeŕg¹,

Blank²,

Nöth³

et al. 1999

Angew. Chem. Int. Ed.

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“…As recently reported, [1,2] the reaction of supersilylsodium NaR* (R* ϭ SitBu 3 ϭ supersilyl) with aluminium trihalides AlX 3 (X ϭ Cl, Br) in alkanes leads, at room temperature, via isolable bis(supersilyl)aluminium halides R* 2 AlX to tetrakis(supersilyl)dialane R* 2 AlϪAlR* 2 (cf. Scheme 1).…”

Section: Introductionmentioning

confidence: 75%

“…In an irreversible reaction it thermolizes to tris(supersilyl)dialanyl R* 3 Al 2 · as well as to tetrakis(supersilyl)cyclotrialanyl R* 4 Al 3 · and to tetrakis(supersilyl)-tetrahedro-tetraalane R* 4 Al 4 (Scheme 1). [2] Possibly, R* 4 Al 3 · forms by a reaction structure analyses of the mentioned compounds, the Ga−Ga bond of the digallanide NaGa 2 R* 3 ×3THF (NMR spectroscopically observed) is comparably short (2.380 Å ), approaching a bond order of 2. In fact, it is distinctly shorter than the Ga−Ga bond (2.420 Å ) in the digallanyl R* 3 Ga 2 · (EPR spectroscopically observed).…”

Section: Introductionmentioning

confidence: 99%

“…Formally, the radical 3 decomposes with elimination of supersilylgallium R*Ga into the digallanyl 2, whereby R*Ga tetramerizes. Because the digallanyl 2 itself decomposes at 100°C in heptane to dark-violet air-and moisture-sensitive, in organic media soluble tetrakis(supersilyl)-tetrahedro-tetragallane (R* 4 Ga 4 ; 4) and (R*) 2 , [4] the trigallanyl 3 finally decomposes in pentane at 100°C exclusively into (R*) 2 …”

mentioning

confidence: 99%

“…The structures of the trigallanyl R* 4 Ga 3 · (3), the digallanide NaGa 2 R* 3 ϫ3THF [2 Ϫ ; cation Na(THF) 3 ϩ ], and the trigallanide [Ga 3 R* 4 ] Ϫ [3 Ϫ ; cation Na(18-C-6)(THF) 2 ϩ ] are shown in the Figures 1, 2, and 3, respectively, together with selected bond lengths and angles. The structure of the digallanyl R* 3 Ga 2 · (2) has already been published.…”

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confidence: 99%

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On the Gallanyls R3Ga2· and R4Ga3· As Well As Gallanides R3Ga2− and R4Ga3− (R* = SitBu3) − Syntheses, Characterization, Structures

Wibeŕg

Blank

Amelunxen

et al. 2001

Eur. J. Inorg. Chem.

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The reduction of black‐blue tris(supersilyl)digallanyl [R*2Ga−GaR*]· (R* = SitBu3 = supersilyl) in organic solvents with Na, NaC10H8, or NaR* leads to deep‐red sodium tris(supersilyl)digallanide−THF(1/3) NaGa2R*3×3THF = [R*2Ga−GaR*Na(THF)3], which transforms in the presence of 18‐crown‐6 into deep‐blue sodium tetrakis(supersilyl)trigallanide−18‐crown‐6(1/1)−THF(1/2) [Na(18‐C‐6)(THF)2]+[R*2Ga−GaR*−GaR*]−.The oxidation of the latter anion with R*Br or TCNE as well as the reaction of the digallanyl R*3Ga2· with R*Br leads to deep‐green tetra(supersilyl)cyclotrigallanyl [···R*Ga−GaR*2−GaR*···]·. The latter radical thermolizes at 100 °C to dark‐violet tetrakis(supersilyl)‐tetrahedro‐tetragallane R*4Ga4 besides the digallanyl R*3Ga2·. This is also prepared from NaR* and GaCl3 or R*2GaCl, as well as by oxidation of R*3Ga2−, and itself thermolizes with formation of the tetrahedrane R*4Ga4. According to X‐ray structure analyses of the mentioned compounds, the Ga−Ga bond of the digallanide NaGa2R*3×3THF (NMR spectroscopically observed) is comparably short (2.380 Å), approaching a bond order of 2. In fact, it is distinctly shorter than the Ga−Ga bond (2.420 Å) in the digallanyl R*3Ga2· (EPR spectroscopically observed). The Ga atoms of the trigallanyl R*4Ga3· (EPR spectroscopically observed) are located at the corners of a triangle with two shorter R*2Ga−GaR* sides (2.527 Å) and a comparably longer R*Ga−GaR* basis (2.879 Å). The mean value of the two Ga−Ga bonds in the trigallanide R*4Ga3− (NMR spectroscopically observed) is as long (2.53 Å) as the short Ga−Ga bonds in R*4Ga3·. The anion shows an intramolecular CH3···Ga contact (C−Ga 2.10 Å) between one peripheral methyl group of the R*2Ga entity and the anionic Ga atom in [R*2Ga−GaR*−GaR*]−.

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Aluminium Hydrazides: Reactions oftert-Butylaluminium Chlorides with Dilithium Bis(trimethylsilyl)hydrazide – Formation of Iminoalanes and their Hydrazido Adducts

Uhl¹,

Molter

Koch

1999

Eur. J. Inorg. Chem.

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Di(tert‐butyl)aluminium chloride reacted with dilithium bis(trimethylsilyl)hydrazide with the formation of a novel Al2Li2N4 cage compound 1. Its structure consists of a dimeric iminoalane RAl(μN–SiMe3)2AlR (R = CMe3), which is bridged by a dilithiumhydrazido ligand with an intact N–N bond. A heterocubane‐type molecule is formed, in which two vertices are occupied by Al atoms, two by Li atoms and four by N atoms. One face of the cube is strongly distorted due to the short N–N distance of the hydrazido group. A similar compound, 3, was formed with bis(neopentyl)aluminium chloride but it was isolated in very poor yield. The reaction of Li2N2(SiMe3)2 with (Me3C)2AlCl in the presence of THF yielded an adduct 2, in which each Li atom of the cage is additionally coordinated via Li–Cl–Al bridges to the ligand (Me3Al)2Cl·THF. The reaction of dilithium bis(trimethylsilyl)hydrazide with tert‐butylaluminium dichloride gave, by complete cleavage of the hydrazido groups, a dimeric iminoalane [Me3C(THF)AlNSiMe3]2 (4), in which each aluminium atom is coordinated to one THF molecule. Its uncoordinated, solvent‐free form 5 was obtained by heating solid 4 to 150 °C in vacuo for several hours. It was identified as the tetrameric iminoalane (Me3CAlNSiMe3)4, which does not adopt the expected heterocubane‐type structure, but consists of three anellated four‐membered Al2N2 heterocycles in a kind of ladder structure. Remarkably, the cage compound 1 could not be obtained by the reaction of an excess of lithium hydrazide with the iminoalanes 4 and 5. All compounds 1–5 were characterized by crystal structure determinations.

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Tetrasupersilyldialuminum [(t-Bu)₃Si]₂Al−Al[Si(t-Bu)₃]₂: The Dialane(4) with the Longest Al−Al Bond to Date^,

Cited by 79 publications

References 13 publications

Dodecaindane (tBu3Si)8In12—A Compound with an In12 Deltapolyhedron Framework

Dodecaindane (tBu3Si)8In12—A Compound with an In12 Deltapolyhedron Framework

On the Gallanyls R3Ga2· and R4Ga3· As Well As Gallanides R3Ga2− and R4Ga3− (R* = SitBu3) − Syntheses, Characterization, Structures

Aluminium Hydrazides: Reactions oftert-Butylaluminium Chlorides with Dilithium Bis(trimethylsilyl)hydrazide – Formation of Iminoalanes and their Hydrazido Adducts

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Tetrasupersilyldialuminum [(t-Bu)3Si]2Al−Al[Si(t-Bu)3]2: The Dialane(4) with the Longest Al−Al Bond to Date,

Cited by 79 publications

References 13 publications

Dodecaindane (tBu3Si)8In12—A Compound with an In12 Deltapolyhedron Framework

Dodecaindane (tBu3Si)8In12—A Compound with an In12 Deltapolyhedron Framework

On the Gallanyls R*3Ga2· and R*4Ga3· As Well As Gallanides R*3Ga2− and R*4Ga3− (R* = SitBu3) − Syntheses, Characterization, Structures

Aluminium Hydrazides: Reactions oftert-Butylaluminium Chlorides with Dilithium Bis(trimethylsilyl)hydrazide – Formation of Iminoalanes and their Hydrazido Adducts

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Tetrasupersilyldialuminum [(t-Bu)₃Si]₂Al−Al[Si(t-Bu)₃]₂: The Dialane(4) with the Longest Al−Al Bond to Date^,

On the Gallanyls R3Ga2· and R4Ga3· As Well As Gallanides R3Ga2− and R4Ga3− (R* = SitBu3) − Syntheses, Characterization, Structures