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標題: Electronic and steric factors affecting the formation of four or five-coordinated aluminum complexes: syntheses and crystal structures of some aluminum alkoxides
作者: Lin, C.H.
Ko, B.T.
Wang, F.C.
Lin, C.C.
Kuo, C.Y.
關鍵字: aluminum;ether alcohol;bifunctional;2-phenoxyethanol;2-methoxybenzyl;alcohol;diels-alder reactions;alkylaluminum;derivatives;spectroscopy;reagents;ketones;amides;al
Project: Journal of Organometallic Chemistry
期刊/報告no:: Journal of Organometallic Chemistry, Volume 575, Issue 1, Page(s) 67-75.
The reaction of 2-phenoxyethanol with AlX3 affords a five-coordinated dimeric product [(mu-OCH2CH2OPh)AlX2](2) (1, X = Cl; 2, X = Br) in high yields. However, the reaction of 2-phenoxyethanol with Al(Bu-i)(3), yields a four-coordinated dimeric product [(mu-O(CH2)(2)OPh)Al(Bu-i)(2)](2), (3). A mixture, [(mu-O(CH2)(2)OPh)Al(Et)(0.75)(Cl)(1.25)](2) (4) is Obtained from the reaction of 2-phenoxyethanol with one equivalent of Et2AlCl. The reaction of 2-methoxybenzyl alcohol with AlR3 gives a semi-pentacoordinated dimeric product [(mu-OCH2C6H4OMe)AlR2](2) (5, R = Me; 6, X = Bu-i) in high yields. Crystal structure studies of these compounds reveal that the distance between Al and the phenoxy oxygen or the methoxy oxygen is 3 > 6 > 5 much greater than 4 > 1 similar to 2. Although both the electronic and steric effect influence the nature of the O,O'-bifunctional ligand chelating on the aluminum center to generate a five- or four-coordinated aluminum, the electronic effect is considered to play a major role. The interaction of aluminum and ethereal oxygen can be monitored by C-13-NMR spectroscopic studies. (C) 1999 Elsevier Science S.A. All rights reserved.
ISSN: 0022-328X
DOI: 10.1016/s0022-328x(98)00968-1
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