State Key Laboratory of Molecular Engineering of Polymers, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai, 200433, P.R. China.
Chemistry. 2018 Jul 20;24(41):10357-10363. doi: 10.1002/chem.201801381. Epub 2018 Jul 4.
p-Methoxybenzeneazo-substituted o-carboranes have been synthesized and their reactivity with half-sandwich iridium and rhodium complexes has been investigated in detail. A variety of solvent- and base-dependent, highly site-selective B-H and C-C σ-bond activations at the C/B cage have been observed. While the use of CH OH leads to the formation of metallacarboranes, o-carborane clusters undergo cyclometallation reactions involving B(6)-H, B(4)-H or a rare B(7)-H activation in CH Cl . The synthesis of a unique pseudo-closo-iridacarborane through a very unconventional metal-mediated C -C activation is described in this contribution.
对位甲氧基苯偶氮取代的邻-碳硼烷已被合成，并详细研究了它们与半三明治铱和铑配合物的反应性。观察到在 C/B 笼中，溶剂和碱依赖性的各种高度选择性的 B-H 和 C-C σ 键的活化。虽然使用 CH3OH 导致金属碳硼烷的形成，但邻-碳硼烷簇经历涉及 B(6)-H、B(4)-H 或 B(7)-H 活化的环金属化反应在 CH2Cl2 中。本贡献中描述了通过非常非常规的金属介导的 C-C 活化合成独特的假closo-iridacarborane。
