Cui Peng-Fei, Lin Yue-Jian, Jin Guo-Xin
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.
Dalton Trans. 2017 Nov 14;46(44):15535-15540. doi: 10.1039/c7dt03529b.
A 16-electron half-sandwich Ir(iii) complex (CpIr(SCN-Ph)CHH, 2) featuring an o-carboranylthioamidate ligand has been synthesized, and its reactivity has been studied in detail. 2 reacts with donor ligands to afford a stable 18-electron configuration. Interestingly, the electron-deficient iridium complex 2 underwent an Ir-S bond insertion reaction with DMAD to produce an acetylene insertion product 5. Complex 2 also reacted with the [CpIr] unit, produced by the reaction between [Cp*IrCl] and AgOTf, to form a unique binuclear species with a metal-metal bond. Moreover, a selective B(6)-H bond activation of the o-carborane complex has also been achieved.
已合成出一种具有邻碳硼烷硫代酰胺配体的16电子半夹心铱（III）配合物（CpIr(SCN-Ph)CHH，2），并对其反应活性进行了详细研究。2与供体配体反应可得到稳定的18电子构型。有趣的是，缺电子铱配合物2与DMAD发生Ir-S键插入反应生成乙炔插入产物5。配合物2还与[CpIrCl]和AgOTf反应生成的[Cp*Ir]单元反应，形成具有金属-金属键的独特双核物种。此外，还实现了邻碳硼烷配合物的选择性B(6)-H键活化。
