Syntheses and Surprising Regioselectivity of 5- and 6-Substituted Decaboranyl Ethers via the Nucleophilic Attack of Alcohols on 6- and 5-Halodecaboranes

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• 作者：William C. Ewing ; Patrick J. Carroll ; Larry G. Sneddon
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 2, 2011
• 年：2011
• 卷：50
• 期：9
• 页码：4054-4064
• 全文大小：1246K
• 年卷期：v.50,no.9(May 2, 2011)
• ISSN：1520-510X

文摘

The selective syntheses of new classes of decaboranyl ethers containing a range of functional groups substituted at the B5 or B6 positions were achieved through the reaction of alcohols with halodecaboranes. The surprising regioselectivity of the reaction, where the reaction of the 6-halodecaboranes (6-X-B₁₀H₁₃) with alcohols yielded the 5-substituted decaboranyl ethers (5-RO-B₁₀H₁₃) and the reaction with 5-halodecaboranes (5-X-B₁₀H₁₃) gave the 6-substituted decaboranyl ethers (6-RO-B₁₀H₁₃), was confirmed by NMR and X-ray crystallographic analyses. The crystallographic determinations also showed that the decaboranyl ethers had shortened B鈭扥 bonds and apparent sp² hybridization at oxygen indicating significant 蟺-backbonding from oxygen to the cage boron. A possible substitution mechanism was computationally identified involving: (1) initial nucleophilic attack by the alcohol鈭抩xygen at a site adjacent to the 5- or 6-halo-substituted boron, (2) movement of the terminal hydrogen at the point of attack to a bridging position, (3) formation of a 5-membered (B鈭扥鈭扝鈭扖l鈭払) cyclic transition state allowing the acidic methanolic鈭抙ydrogen to bond to the halogen, (4) release of HX, and finally (5) movement of a bridging hydrogen into the vacated terminal position. Deuterium labeling studies confirmed the movement of hydrogen from a bridging position of the halodecaborane into the halogen-vacated terminal position on the decaboranyl ether product. The relative reaction rates of the 6-X-B₁₀H₁₃ compounds (X = F, Cl, Br, I) with alcohols were likewise found to be consistent with this mechanism.