Cyclometalated Phosphinine-Iridium(III) Complexes: Synthesis, Reactivity, and Application as Phosphorus-Containing Water-Oxidation Catalysts
Cyclometalated Phosphinine-Iridium(III) Complexes: Synthesis, Reactivity, and Application as Phosphorus-Containing Water-Oxidation Catalysts
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DOI：
10.1021/acs.organomet.5b00281
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发表时间：
2015-06-22
期刊：
影响因子：
2.8
通讯作者：
Mueller, Christian
中科院分区：
文献类型：
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作者：
Broeckx, Leen E. E.;Bucci, Alberto;Mueller, Christian
以[Cp * Ir（（PC）-C-Lambda）Cl]和AgOSO 2CF 3为原料，通过氯化反应合成了新型膦基配合物[Cp * Ir（（PC）-C-Lambda）（CH 3CN）] CF 3SO 3（PC）-C-Lambda =环化2，4，6-三苯基膦），并对其进行了晶体学表征.结果表明，该物种是第一个含磷的Ir（III）配合物，其在硝酸铈铵驱动的水氧化反应中显示出显着的活性。原位NMR光谱研究进一步揭示了水被选择性地添加到P-C双键之一，形成四种立体异构体。此外，[Cp*Ir（（PC）-C-Lambda）]物质，可能是OH-官能化的，但仍然具有同时结合到铱的Cp* 和（PC）-C-Lambda-配体，甚至在催化条件下也存在于溶液中。
The novel phosphinine-based coordination compound [Cp*Ir((PC)-C-Lambda)(CH3CN)]CF3SO3 ((PC)-C-Lambda = cyclometalated 2,4,6-triphenylphosphinine) could be synthesized by chloride abstraction from [Cp*Ir((PC)-C-Lambda)Cl] with AgOSO2CF3 and crystallographically characterized. It turned out that this species is the first phosphorus-containing Ir(III) complex which shows a remarkable activity in the cerium ammonium nitrate driven water oxidation reaction. In situ NMR spectroscopic investigations further reveal that water is added selectively to one of the P-C double bonds with formation of four stereoisomers. Moreover, [Cp*Ir((PC)-C-Lambda)] species, possibly OH-functionalized but still having Cp* and (PC)-C-Lambda-ligands contemporary bound to iridium, are present in solution, even under catalytic conditions.