Reactions of 1,3,2‐Diselenaphospholanes with Lewis Acids: Borane and (Pentamethylcyclopentadienyl)rhodium and ‐iridium Dichloride
作者:Bernd Wrackmeyer、Elena V. Klimkina、Wolfgang Milius
DOI:10.1002/ejic.201402486
日期:2014.10
an annelated 1,2-dicarba-closo-dodecaborane(12) unit were treated with Lewis acids such as borane reagents (BH3 in THF, and BH3–SMe2) as well as Cp*-rhodium and -iridium dichloride (Cp* = pentamethylcyclopentadienyl). In all cases, the adduct formation in the beginning was followed by ring expansion through insertion of the borane or Cp*MCl2 into one of the P–Se bonds accompanied by transfer of a hydrido
2-R-1,3,2-二硒代膦烷 (R = iPr, Ph) 与一个退火的 1,2-dicarba-closo-ddecaborane(12) 单元用路易斯酸处理,如硼烷试剂(THF 中的 BH3 和 BH3 –SMe2) 以及 Cp*-铑和-二氯化铱(Cp* = 五甲基环戊二烯基)。在所有情况下,加合物在开始时形成之后,通过将硼烷或 Cp*MCl2 插入 P-Se 键之一,伴随着氢化或氯配体转移到磷而发生环扩张。最后,P-R 单元从环上移开得到交换产物,其中硼或金属已成为五元环的一部分。通过NMR光谱(1H、11B、13C、31P和77Se)监测反应。发现提出的反应序列与计算的 [B3LYP/6-311+G(d,p), LANL2DZ (Rh, Ir) 理论水平] 各种产品的优化气相结构的相对能量。通过 X 射线分析确定了具有 M = Ir、R = iPr 的优选插入产物的新分子结构。