Unfairly Forgotten Member of the Iodocarborane Family: Synthesis and Structural Characterization of 8-Iodo-1,2-dicarba-closo-dodecaborane, Its Precursors, and Derivatives.
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- 作者：Alexander V. Safronov ; Yulia V. Sevryugina ; Satish S. Jalisatgi ; Robert D. Kennedy ; Charles L. Barnes ; M. Frederick Hawthorne
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：February 20, 2012
- 年：2012
- 卷：51
- 期：4
- 页码：2629-2637
- 全文大小：515K
- 年卷期：v.51,no.4(February 20, 2012)
- ISSN：1520-510X
文摘
8-Iodo-1,2-dicarba-closo-dodecaborane (7) was prepared in three steps starting from decaborane-14 with 20% overall yield. In the presence of nucleophiles, compound 7 undergoes selective removal of the boron vertex in the position para to the iodine substituent to form the anionic nido-carborane 1-iodo-7,8-dicarba-nido-undecaborate. Capping of the corresponding dicarbollide dianion with BI3 led to formation of the new carborane, 3,10-diiodo-1,2-dicarba-closo-dodecaborane (15). The same dicarbollide dianion reacts with cobalt and nickel acetylacetonates in anhydrous tetrahydrofuran to form the corresponding bis(dicarbollide) complexes with excellent yields. All compounds were characterized by multinuclear NMR and high-resolution mass spectroscopy. Structures of 2-iododecaborane (2), 8-iodo-1,2-dicarba-closo-dodecaborane (7), 1-ethoxycarbonyl-8-iodo-1,2-dicarba-closo-dodecaborane (10), cesium 1-iodo-7,8-dicarba-nido-undecaborate (13), 3,10-diiodo-1,2-dicarba-closo-dodecaborane (15), and cesium 3,3鈥?commo-(10-iodo-1,2-dicarba-3-cobalta-closo-dodecaborane)-(10鈥?iodo-1鈥?2鈥?dicarba-3鈥?cobalta-closo-dodecaborane) (16) were established by X-ray analysis of single crystals.