Ewing William C, Carroll Patrick J, Sneddon Larry G
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
Inorg Chem. 2008 Oct 6;47(19):8580-2. doi: 10.1021/ic801288e. Epub 2008 Aug 29.
The high-yield syntheses of 6-X-B 10H 13 [X = Cl (88%), Br (96%), I (84%)] resulted from the cage-opening reactions of the (NH 4 (+)) 2B 10H 10 (2-) salt with ionic-liquid-based superacidic hydrogen halides, while both the previously unknown 6-F-B 10H 13 (77%) derivative and 6-Cl-B 10H 13 (90%) were synthesized in high yields via the reactions of (NH 4 (+)) 2B 10H 10 (2-) with triflic acid in the presence of 1-fluoropentane and dichloromethane, respectively. Structural characterizations of 1- 4 confirm the predicted structures and indicate strong halogen back-bonding interactions with the B6 boron. The reaction of 6-Br-B 10H 13 with Bu 3SnH produced the parent B 10H 14 in 70% yield, and thus, this reaction, in conjunction with the haloacid-induced closo-B 10H 10 (2-) cage-opening reactions, has the potential to provide an alternative to the traditional diborane pyrolysis route to decaborane.
6-X-B₁₀H₁₃（X = Cl（88%）、Br（96%）、I（84%））的高产率合成是通过(NH₄⁺)₂B₁₀H₁₀²⁻盐与离子液体基超强酸性卤化氢的开笼反应实现的，而此前未知的6-F-B₁₀H₁₃（77%）衍生物和6-Cl-B₁₀H₁₃（90%）则分别通过在1-氟戊烷和二氯甲烷存在下(NH₄⁺)₂B₁₀H₁₀²⁻与三氟甲磺酸的反应高产率合成。1-4的结构表征证实了预测的结构，并表明与B6硼存在强烈的卤素反馈键相互作用。6-Br-B₁₀H₁₃与Bu₃SnH反应以70%的产率生成母体B₁₀H₁₄，因此，该反应与卤酸诱导的闭式B₁₀H₁₀²⁻开笼反应相结合，有可能为传统的二硼烷热解制备癸硼烷路线提供一种替代方法。
