Dichlorotetrakis(tetrahydrofuran)aluminium trichloroethylaluminate

Sluka, Radek; Nečas, Marek; Šindelář, Pavel

doi:10.1107/s1600536804006312

Cited by 4 publications

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“…As can be gathered from Figure , 6 is an ionic compound with a trinuclear cation and chloride anion. This result corresponds with a low temperature of crystallization, which in the XAlCl 2 -THF systems (X = Me, Cl) favored the ionic forms [Al(THF) 4 ][XAlCl 3 ] over the neutral adducts [XAlCl 2 (THF) 2 ] . The molecule of 6 features a centrosymmetric trinuclear Al(μ-O) 2 Al(μ-O) 2 Al core with two fused four-membered rings and all three Al atoms octahedrally coordinated.…”

Section: Resultsmentioning

confidence: 95%

A Structurally Diverse Series of Aluminum Chloride Alkoxides [Cl_xAl(μ-OR)_y]_n (R = ⁿBu, ^cHex, Ph, 2,4-^tBu₂C₆H₃)

Moravec

Sluka²,

Nečas³

et al. 2009

Inorg. Chem.

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A diverse series of aluminum chloride alkoxides, [Cl(x)Al(mu-OR)(y)](n) (R = (n)Bu, (c)Hex, Ph, 2,4-(t)Bu(2)C(6)H(3)), was synthesized using the reactions of dichlorethylalane (EtAlCl(2)) with cyclohexanol ((c)HexOH), n-butanol ((n)BuOH), and phenols (PhOH and 2,4-(t)Bu(2)C(6)H(3)OH). Eight molecular products were isolated and structurally characterized. The dimeric [Cl(2)Al(mu-O(c)Hex)(2)AlCl(2)] (1) was the smallest oligomer isolated among the cyclohexanolate derivatives. The adduct of 1 with cyclohexanol is a dinuclear molecule [Cl(2)(HO(c)Hex)Al(mu-O(c)Hex)(2)AlCl(2)] (2) which represents a possible intermediate in the conversion reaction leading to the formation of a trinuclear bicyclic [ClAl{(mu-O(c)Hex)(2)AlCl(2)}(2)] (3). Two polymorphic forms of 3 were isolated. Further coordination of cyclohexanol to the Lewis acidic five-coordinate aluminum atom in 3 provided [Cl(HO(c)Hex)Al{(mu-O(c)Hex)(2)AlCl(2)}(2)] (4) with octahedrally coordinated central aluminum. Compound 4 could be regarded as a precursor to the well-known Mitsubishi (tridiamond) tetranuclear species. The reactions of EtAlCl(2) with less sterically demanding (n)BuOH yielded a cyclic trimer, [Cl(2)Al(mu-O(n)Bu)](3) (5), and a unique trinuclear ionic species, [Cl(2)Al{(mu-OH)(mu-O(n)Bu)AlCl(HO(n)Bu)(3)}(2)]Cl (6) with a linear Al(mu-O)(2)Al(mu-O)(2)Al core. In the reactions with phenols, the aromatic groups preferentially stabilized dimeric structures of [Cl(2)Al(mu-OR)(2)AlCl(2)] (R = Ph, 7; 2,4-(t)Bu(2)C(6)H(3), 8). Since these compounds could be considered as intermediates in the nonhydrolytic condensation reactions of metal halides with metal alkoxides, a mixture of EtAlCl(2) with (c)HexOH was used as a precursor for the nonaqueous synthesis of alumina by alkylhalide elimination.

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Section: Resultsmentioning

confidence: 95%

A Structurally Diverse Series of Aluminum Chloride Alkoxides [Cl_xAl(μ-OR)_y]_n (R = ⁿBu, ^cHex, Ph, 2,4-^tBu₂C₆H₃)

Moravec

Sluka²,

Nečas³

et al. 2009

Inorg. Chem.

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“…Various unique bimetallic aluminum cations have been isolated adventitiously. When SalenTiCl 2 is combined with AlMe 3 , a low yield (∼5%) transmetalation occurs where the Salen ligand is displaced from titanium and [Salen-(AlMe)(AlMe 2 )][AlCl 3 Me] ( [128][AlCl 3 Me]) results (Figure 30). 124 In the structure, the central Al atom is in a highly distorted geometry that is hard to classify as either tbp or sqpy.…”

Section: Aluminum Cationsmentioning

confidence: 99%

“…salts with L ) thf, 127 thf (with EtAlCl 3 as the anion), 128 pyridine, 129 NH 3 , 130 etc. These cations would correspond to the type A class of cations (Figure 32).…”

Section: Introductionmentioning

confidence: 99%

“…Aluminum cations with six ligands can be readily prepared by base-assisted heterogeneous cleavage of the [AlCl 3 ] 2 dimer. This produces cations of the formula AlCl 2 (L) 4 + as AlCl 4 − salts with L = thf, thf (with EtAlCl 3 − as the anion), pyridine, NH 3 , etc. These cations would correspond to the type A class of cations (Figure ).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, and Applications of Group 13 Cationic Compounds

2008

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Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions

Olaru

Duvinage

Lork

et al. 2019

Chemistry A European J

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Fluoride abstraction from bis‐m‐terphenylelement fluorides (2,6‐Mes2C6H3)2EF (E=P, As) generated the highly reactive phosphenium ion [(2,6‐Mes2C6H3)2P]+ and the arsenium ion [(2,6‐Mes2C6H3)2As]+, which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]phospholium ion and an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho‐position of a flanking mesityl group to the meta‐position. This reactivity of [(2,6‐Mes2C6H3)2E]+ (E=P, As) is in sharp contrast to the related stibenium ion [(2,6‐Mes2C6H3)2Sb]+ and bismuthenium ion [(2,6‐Mes2C6H3)2Bi]+, which have been recently isolated and fully characterized (Angew. Chem. Int. Ed. 2018, 57, 10080–10084). On the basis of DFT calculations, a mechanism for the rearrangement of the phosphenium and arsenium ions into the phospholium and arsolium ions is proposed, which is not feasible for the stibenium and bismuthenium ions.

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Dichlorotetrakis(tetrahydrofuran)aluminium trichloroethylaluminate

Abstract: Key indicatorsSingle-crystal X-ray study T = 120 K Mean '(C±C) = 0.004 A Ê R factor = 0.036 wR factor = 0.096 Data-to-parameter ratio = 17.1For details of how these key indicators were automatically derived from the article, see

Cited by 4 publications

References 5 publications

A Structurally Diverse Series of Aluminum Chloride Alkoxides [Cl_xAl(μ-OR)_y]_n (R = ⁿBu, ^cHex, Ph, 2,4-^tBu₂C₆H₃)

A Structurally Diverse Series of Aluminum Chloride Alkoxides [Cl_xAl(μ-OR)_y]_n (R = ⁿBu, ^cHex, Ph, 2,4-^tBu₂C₆H₃)

Synthesis, Characterization, and Applications of Group 13 Cationic Compounds

Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions

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Dichlorotetrakis(tetrahydrofuran)aluminium trichloroethylaluminate

Abstract: Key indicatorsSingle-crystal X-ray study T = 120 K Mean '(C±C) = 0.004 A Ê R factor = 0.036 wR factor = 0.096 Data-to-parameter ratio = 17.1For details of how these key indicators were automatically derived from the article, see

Cited by 4 publications

References 5 publications

A Structurally Diverse Series of Aluminum Chloride Alkoxides [ClxAl(μ-OR)y]n (R = nBu, cHex, Ph, 2,4-tBu2C6H3)

A Structurally Diverse Series of Aluminum Chloride Alkoxides [ClxAl(μ-OR)y]n (R = nBu, cHex, Ph, 2,4-tBu2C6H3)

Synthesis, Characterization, and Applications of Group 13 Cationic Compounds

Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions

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A Structurally Diverse Series of Aluminum Chloride Alkoxides [Cl_xAl(μ-OR)_y]_n (R = ⁿBu, ^cHex, Ph, 2,4-^tBu₂C₆H₃)

A Structurally Diverse Series of Aluminum Chloride Alkoxides [Cl_xAl(μ-OR)_y]_n (R = ⁿBu, ^cHex, Ph, 2,4-^tBu₂C₆H₃)