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Unusual Closure of the Ten-Vertex Nido Cage via Alkylation: Regiospecific Synthesis of 3-Alkyl Derivatives of closo-1,2-C2B8H10
Inorganic Chemistry ( IF 4.6 ) Pub Date : 2018-01-05 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02783
Mario Bakardjiev 1 , Bohumil Štíbr 1 , Oleg L. Tok 1 , Josef Holub 1
Affiliation  

Alkylation of the [nido-5,6-R12C2B8H9] anions (where R1 = H and Me) with alkyl halides (RX, where R = primary and secondary alkyls) in boiling tetrahydrofuran (THF) proceeds via unusual H2 elimination, followed by cage closure to give a series of the neutral closo-1,2-R12C2B8H7-3-R derivatives in ∼70–80% yields. In contrast, treatment of the unsubstituted [nido-5,6-C2B8H11] anion with tert-butyl bromide (t-BuBr) led to the formation of the parent closo-1,2-C2B8H10 in >85% yield. The constitution of all compounds isolated has been confirmed unambiguously by multinuclear (11B, 1H, and 13C) nuclear magnetic resonance measurements and α-shift correlation assessments.

中文翻译:

的3烷基衍生物特异合成:通过烷基化的十顶点尼多笼的不寻常的封闭closo- 1,2--C 28 ħ 10

[ nido -5,6 -R 1 2 C 2 B 8 H 9 ] -阴离子(其中R 1 = H和Me)与烷基卤化物(RX,其中R =伯和仲烷基)在沸腾的四氢呋喃(THF)中进行烷基化)通过异常的H 2消除过程进行,然后关闭笼子,以约70-80%的产率得到一系列中性closo -1,2-R 1 2 C 2 B 8 H 7 -3-R衍生物。相反,未取代的[ nido -5,6 -C 2 B 8 H 11 ]的处理丁基溴化物(t -BuBr)形成阴离子,以> 85%的收率形成母体closo -1,2-C 2 B 8 H 10。通过多核(11 B,1 H和13 C)核磁共振测量和α位移相关性评估已明确确认了所有分离出的化合物的组成。
更新日期:2018-01-05
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