Aluminum complexes containing cyclohexane-1,2-diyl linked bis(ketiminato) ligands and proton-promoted demethylation

Chun Hsueh Huang, Li Feng Hsueh, Pei Cheng Kuo, Man Lee Hon, Chia Liang Uno, Jui Hsien Huang, Cheng Yi Tu, Ching Han Hu, Gene Hsiang Lee, Cheng Hsiung Hung

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Abstract

A series of cyclohexane-1,2-diyl linked bis(ketiminato)aluminum complexes were synthesized. Reaction of a mixture of cis- and trans-diaminocyclohexane and 2,4-pentanedione gave a mixture of cis- and trans-cyclohexane-1,2-diyl linked bis(ketimine) ligands (cis-1 and trans-1), which can be separated by fractional recrystallization. Reactions of trans-1 with 1 and 2 equiv. AlMe3 gave monoaluminum complex trans-C6H10[(NCMeCHCMeO)AlMe 2](NHCMeCHCMeO) (2) and dialuminum complex trans-C6H 10[(NCMeCHCMeO)AlMe2]2 (3), respectively. Contrarily, when 1 equiv. or excess cis-1 reacted with AlMe3, only five-coordinate, linked bis(ketiminato) aluminum complex cis-C6H 10[(NCMeCHCMeO)2AlMe] (4) could be isolated in moderate yield. Heating complex 2 at reflux in a toluene solution resulted in the elimination of 1 equiv. methane to generate a five-coordinate, linked bis-(ketiminato)aluminum complex, trans-C6H10[(NCMeCHCMeO) 2AlMe] (5). Complex 2 reacts with allyl alcohol and 2,6-dimethylphenol to form dimeric aluminum complexes [trans-C6H 10(NCMeCHCMeO)2Al]2(μ-O-CH 2CH=CH2)2 (6) and trans-C6H 10(NCMeCHCMeO)2Al(O-C6H3-2,6-Me 2) (7), respectively. All the complexes have been characterized by 1H and 13C NMR spectroscopy and X-ray diffractometry.

Original languageEnglish
Pages (from-to)3000-3008
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number19
DOIs
Publication statusPublished - 2008 Jul 1

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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