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|標題:||Conformation of heterocycles controlled by the existence of unusual C-H center dot center dot center dot X hydrogen bonds: Syntheses and structure determination of aluminum aryloxides||作者:||Ko, B.T.
|關鍵字:||crystal-structures;h...o||Project:||Inorganic Chemistry||期刊/報告no：:||Inorganic Chemistry, Volume 39, Issue 7, Page(s) 1463-1469.||摘要:||
The reactions of AlMe3 in diethyl ether with 1 molar equiv of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (MMBP-H-2), 2,2'-methylenebis(4,6-di-tert-butylphenol) (MDBP-H-2), and 2,2'-ethylidenebis(4,6-di-tert-butylphenol) (EDBP-H-2) afford series of four-coordinate monomeric aluminum aryloxides, MeAl(O similar to O)(OEt2), 1-3 (1, (O similar to O) = MMBP; 2, (O similar to O) = MDBP; 3, (O similar to O) = EDBP). In THF, 1 molar equiv of EDBP-H2 reacts with AlMe3 to provide the THF-coordinated complex MeAl(EDBP)(THF) 4. However, in the absence of a coordinating solvent, the reaction of EDBP-H2 with AlMe3 yields the dimeric complex [MeAl(mu-EDBP)](2) (5). Complex 5 further reacts with Et4NCl, Et4NBr, and Ph3PO to afford the corresponding monomeric ionic complex [Et4N][MeAl(EDBP)(X)] (6, X = Cl; 7, X = Br) and the neutral complex [MeAl(EDBP)(O=PPh3)] (8), respectively. Complexes 1, 2, 4 and 6-8 are subjected to X-ray structure analyses, and the solid state structures reveal that the conformations of the eight-membered heterocycles are governed by the formation of the unusual C-H ... X hydrogen bonds.
|Appears in Collections:||化學系所|
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