Functionalized o-carboranes are interesting ligands for transition metals. Reaction of LiC2B10H11 with Me2NCH2CH2Cl in toluene afforded 1-Me2NCH2CH2-1,2-C2B10H11
(1). Treatment of 1 with 1 equiv. of n-BuLi gave [(Me2NCH2CH2)C2B10H10]Li ([1]Li), which was a very useful synthon for the production of bisfunctional o-carboranes. Reaction of [1]Li with RCH2CH2Cl afforded 1-Me2NCH2CH2-2-RCH2CH2-1,2-C2B10H10
(R = Me2N (2), MeO (3)). 1 and 2 were also prepared from the reaction of Li2C2B10H10 with excess Me2NCH2CH2Cl. Treatment of [1]Li with excess MeI or allyl bromide gave the ionic salts, [1-Me3NCH2CH2-2-Me-1,2-C2B10H10][I]
(4) and [1-Me2N(CH2CHCH2)CH2CH2-2-(CH2CHCH2)-1,2-C2B10H10][Br]
(6), respectively. Interaction of [1]Li with 1 equiv. of allyl bromide afforded 1-Me2NCH2CH2-2-(CH2CHCH2)-1,2-C2B10H10
(5). Treatment of [1]Li with excess dimethylfulvene afforded 1-Me2NCH2CH2-2-C5H5CMe2-1,2-C2B10H10
(7). Interaction of [1]Li with excess ethylene oxide afforded an unexpected product 1-HOCH2CH2-2-(CH2CH)-1,2-C2B10H10
(8). 1 and 3 were conveniently converted into the corresponding deborated compounds, 7-Me2NHCH2CH2-7,8-C2B9H11
(9) and 7-Me2NHCH2CH2-8-MeOCH2CH2-7,8-C2B9H10
(10), respectively, in MeOH–MeOK solution. All of these compounds were characterized by various spectroscopic techniques and elemental analyses. The solid-state structures of 4 and 6–10 were confirmed by single-crystal X-ray analyses.
功能化的邻卡巴烷是过渡
金属的有趣
配体。在
甲苯中,LiC2B10H11与Me2NCH2CH2Cl的反应生成了1-Me2NCH2CH2-1,2-C2B10H11(1)。将1与1当量的n-BuLi处理,得到[(Me2NCH2CH2)C2B10H10]Li([1]Li),这是生产双功能邻卡巴烷的非常有用的合成中间体。[1]Li与RCH2CH2Cl的反应生成了1-Me2NCH2CH2-2-RCH2CH2-1,2-C2B10H10(R = Me2N(2),MeO(3))。1和2也可以通过Li2C2B10H10与过量Me2NCH2CH2Cl的反应制备。将[1]Li与过量的MeI或烯丙基
溴处理,分别得到离子盐[1-Me3NCH2CH2-2-Me-1,2-C2B10H10][I](4)和[1-Me2N(CH2CHCH2)CH2CH2-2-(CH2CHCH2)-1,2-C2B10H10][Br](6)。[1]Li与1当量的烯丙基
溴反应生成了1-Me2NCH2CH2-2-(CH2CHCH2)-1,2-C2B10H10(5)。将[1]Li与过量的二甲基富烯反应,得到1-Me2NCH2CH2-2-C5H5CMe2-1,2-C2B10H10(7)。[1]Li与过量的
环氧乙烷反应,生成了意外产物1-HOCH2CH2-2-(CH2CH)-1,2-C2B10H10(8)。1和3可以方便地转化为相应的脱
硼化合物,分别为7-Me2NHCH2CH2-7,8-C2
B9H11(9)和7-Me2NHCH2CH2-8-MeOCH2CH2-7,8-C2
B9H10(10),反应在MeOH–MeOK溶液中进行。所有这些化合物都通过各种光谱技术和元素分析进行表征。4和6–10的固态结构通过单晶X射线分析得到了确认。