A Structurally Diverse Series of Aluminum Chloride Alkoxides [ClxAl(m-OR)y]n (R = nBu, cHex, Ph, 2.4-tBu2C6H3)

MORAVEC, Zdeněk, Radek SLUKA, Marek NEČAS, Vojtěch JANČÍK and Jiří PINKAS. A Structurally Diverse Series of Aluminum Chloride Alkoxides [ClxAl(m-OR)y]n (R = nBu, cHex, Ph, 2.4-tBu2C6H3). INORGANIC CHEMISTRY. Spojené státy americké: American Chemical Society, Washington DC, 2009, vol. 48, No 17, p. 8106-8114. ISSN 0020-1669.

Basic information

• Original name: A Structurally Diverse Series of Aluminum Chloride Alkoxides [ClxAl(m-OR)y]n (R = nBu, cHex, Ph, 2.4-tBu2C6H3)
• Name in Czech: Strukturně bohatá série chloro-alkoxidů hliníku [ClxAl(m-OR)y]n (R = nBu, cHex, Ph, 2.4-tBu2C6H3)
• Authors: MORAVEC, Zdeněk (203 Czech Republic, guarantor), Radek SLUKA (203 Czech Republic), Marek NEČAS (203 Czech Republic), Vojtěch JANČÍK (203 Czech Republic) and Jiří PINKAS (203 Czech Republic).
• Edition: INORGANIC CHEMISTRY, Spojené státy americké, American Chemical Society, Washington DC, 2009, 0020-1669.

Other information

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10402 Inorganic and nuclear chemistry
• Country of publisher: United States of America
• Confidentiality degree: is not subject to a state or trade secret
• Impact factor: Impact factor: 4.657
• RIV identification code: RIV/00216224:14310/09:00029642
• Organization unit: Faculty of Science
• UT WoS: 000269313500014
• Keywords in English: aluminum chloride alkoxides

Abstract

A diverse series of aluminum chloride alkoxides, [ClxAl(m-OR)y]n (R=nBu, cHex, Ph, 2,4-tBu2C6H3), was synthesized using the reactions of dichlorethylalane (EtAlCl2) with cyclohexanol (cHexOH), n-butanol (nBuOH), and phenols (PhOH and 2,4-tBu2C6H3OH). Eight molecular products were isolated and structurally characterized. The dimeric [Cl2Al(m- OcHex)2AlCl2] (1) was the smallest oligomer isolated among the cyclohexanolate derivatives. The adduct of 1 with cyclohexanol is a dinuclear molecule [Cl2(HOcHex)Al(m-OcHex)2AlCl2] (2) which represents a possible intermediate in the conversion reaction leading to the formation of a trinuclear bicyclic [ClAl{(m-OcHex)2AlCl2}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(HOcHex)Al{(m-OcHex)2AlCl2}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 EtAlCl2 with less sterically demanding nBuOH yielded a cyclic trimer, [Cl2Al(m-OnBu)]3 (5), and a unique trinuclear ionic species, [Cl2Al{(m-OH)(m- OnBu)AlCl(HOnBu)3}2]Cl (6) with a linear Al(m-O)2Al(m-O)2Al core. In the reactions with phenols, the aromatic groups preferentially stabilized dimeric structures of [Cl2Al(m-OR)2AlCl2] (R = Ph, 7; 2,4-t Bu2C6H3, 8). Since these compounds could be considered as intermediates in the nonhydrolytic condensation reactions of metal halides with metal alkoxides, a mixture of EtAlCl2 with cHexOH was used as a precursor for the nonaqueous synthesis of alumina by alkylhalide elimination.

Abstract (in Czech)

Reakcemi EtAlCl2 s alkoholy byla připravena a strukturně charakterizována řada nových chloro-alkoxidů hliníku.

Links

• GA203/08/1111, research and development project: Name: Syntéza a vlastnosti anorganicko-organických polymerních materiálů

Investor: Czech Science Foundation, Synthesis and properties of inorganic-organic polymeric materials

• MSM0021622410, plan (intention): Name: Fyzikální a chemické vlastnosti pokročilých materiálů a struktur

Investor: Ministry of Education, Youth and Sports of the CR, Physical and chemical properties of advanced materials and structures