Confirmation of Bridging N-Indolides in 3-Methylindole and Di- and Tri(3-methylindolyl)methane Complexes of Dimethyl-, Diethyl-, and Diisobutylaluminum
Confirmation of Bridging N-Indolides in 3-Methylindole and Di- and Tri(3-methylindolyl)methane Complexes of Dimethyl-, Diethyl-, and Diisobutylaluminum
复制标题
DOI：
10.1021/om100781k
复制
发表时间：
2010-10
期刊：
影响因子：
2.8
通讯作者：
Nicholas B. Kingsley;K. Kirschbaum;M. R. Mason
中科院分区：
文献类型：
--
作者：
Nicholas B. Kingsley;K. Kirschbaum;M. R. Mason
3-甲基吲哚与一等量的R3Al反应生成n -吲哚烯桥接二聚体[(3-CH3C8H5N)AlR2]2 (R = Me (3a), Et （3b), iBu (3c)）。核磁共振波谱（1H, 13C）表明，化合物3a， 3b和3c分别以相互转化的正异构体和反异构体的混合物存在于溶液中。二（3-甲基lindolyl）甲烷或三（3-甲基lindolyl）甲烷与Me3Al或Et3Al的等量反应同样生成n -吲哚烷桥接化合物[(Ph)HC(3- ch3c8h4nalr2)2] （R = Me(4)）或[HC(3- ch3c8h4nalr2)3] (R = Me （5a), Et (5b)）。三（3-甲基-2-吲哚基）甲烷与一等量的iBu3Al反应生成n -吲哚烷桥接化合物[HC(3-CH3C8H4NAliBu2)2(3-CH3C8H4NAl(H)iBu)](6)，显然是每个配合物中一个异丁基的异丁烯被β-氢消除的结果。用x射线晶体学测定了化合物3a、4和5a的分子结构。结晶学数据证实，每种化合物中均存在μ2-η - 1:η - 1- n -3-甲基lindolide基团。
Reactions of 3-methylindole with one equivalent of R3Al produce the N-indolide-bridged dimers [(3-CH3C8H5N)AlR2]2 (R = Me (3a), Et (3b), iBu (3c)). NMR spectroscopy (1H, 13C) demonstrates that compounds 3a, 3b, and 3c each exist in solution as a mixture of interconverting syn and anti isomers. Reactions of di(3-methylindolyl)methane or tri(3-methylindolyl)methane with one equivalent of Me3Al or Et3Al similarly produce the N-indolide-bridged compounds [(Ph)HC(3-CH3C8H4NAlR2)2] (R = Me (4)) or [HC(3-CH3C8H4NAlR2)3] (R = Me (5a), Et (5b)), respectively. Reaction of tri(3-methyl-2-indolyl)methane with one equivalent of iBu3Al yielded the N-indolide-bridged compound [HC(3-CH3C8H4NAliBu2)2(3-CH3C8H4NAl(H)iBu)] (6), apparently the result of β-hydrogen elimination of isobutene from one isobutyl group per complex. The molecular structures of compounds 3a, 4, and 5a were determined by X-ray crystallography. Crystallographic data confirmed the presence of μ2-η1:η1-N-3-methylindolide groups in each compound, the firs...