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|標題:||Intramolecular C-H center dot center dot center dot O hydrogen bond controlling the conformation of heterocycles: synthesis, structure and catalytic reactivity of aluminum aryloxides|
|期刊/報告no：:||Journal of Organometallic Chemistry, Volume 587, Issue 2, Page(s) 151-159.|
|摘要:||The reactions of R2AlX with one equivalent of 2,2'-methylene-bis-(4,6-di-tert-butylphenol) (MDBP-H-2) or 2,2'-methylene-bis(4-methyl-6-tert-butylphenol) (MMBP-H-2) in oxygenated solvent afford monomeric four-coordinated compounds, XAl(MDBP)(S), 1-5 (1: R=Me, X=Br, S=Et2O; 2: R=Et, X=Cl, S=Et2O; 3. R=Me, X=Br, S=THF; 4. R=Et, X = Cl, S = THF; 5: R = X = Et, S = Et2O) or XAl(MMBP)(S), 6-8 (6. R = X = Et, S = Et2O; 7: R = X = Bu-i, S = Et2O; 8: R = Et, X = Cl, S = Et2O). Crystal structures of 1, 2 and 7 demonstrate that the conformation of the eight-membered heterocycles containing aluminum is controlled by an unusual intramolecular C-H ... O hydrogen bond. Et2AlCl or (Bu3Al)-Bu-i reacts with one equivalent of 2, 2'-ethylidene-bis-(4,6-di-tert-butylphenol) (EDBP-H-2) or MDBP-H-2 in toluene giving a dimeric four coordinate compound [CLAL(mu-EDBP](2), 9 or [(BuAl)-Bu-i(mu-MDBP)](2), 10. Some of these compounds have shown great catalytic activities toward the reaction of cycloyentadiene with methacrolein. (C) 1999 Elsevier Science S.A. All rights reserved.|
|Appears in Collections:||化學系所|
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