Cyclometalated Phosphinine鈥揑ridium(III) Complexes: Synthesis, Reactivity, and Application as Phosphorus-Containing Water-Oxidation Catalysts

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• 作者：Leen E. E. Broeckx ; Alberto Bucci ; Cristiano Zuccaccia ; Martin Lutz ; Alceo Macchioni ; Christian M眉ller
• 刊名：Organometallics
• 出版年：2015
• 出版时间：June 22, 2015
• 年：2015
• 卷：34
• 期：12
• 页码：2943-2952
• 全文大小：502K
• ISSN：1520-6041

文摘

The novel phosphinine-based coordination compound [Cp*Ir(P^{鈭?/sup>C)(CH₃CN)]CF₃SO₃ (P鈭?/sup>C = cyclometalated 2,4,6-triphenylphosphinine) could be synthesized by chloride abstraction from [Cp*Ir(P鈭?/sup>C)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鈺怌 double bonds with formation of four stereoisomers. Moreover, [Cp*Ir(P鈭?/sup>C)] species, possibly OH-functionalized but still having Cp* and P鈭?/sup>C-ligands contemporary bound to iridium, are present in solution, even under catalytic conditions.}