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

被引：33

作者：

Broeckx, Leen E. E. ^{[1
]}

Bucci, Alberto ^{[2
,3
]}

Zuccaccia, Cristiano ^{[2
,3
]}

Lutz, Martin ^{[4
]}

Macchioni, Alceo ^{[2
,3
]}

Mueller, Christian ^{[1
,5
]}

机构：

[1] Eindhoven Univ Technol, Chem Engn & Chem, NL-5600 MB Eindhoven, Netherlands

[2] Univ Perugia, Dept Chem Biol & Biotechnol, I-06123 Perugia, Italy

[3] Univ Perugia, CIRCC, I-06123 Perugia, Italy

[4] Univ Utrecht, Bijvoet Ctr Biomol Res Crystal & Struct Chem, NL-3584 CH Utrecht, Netherlands

[5] Free Univ Berlin, Inst Chem & Biochem, D-14195 Berlin, Germany

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 12期

关键词：

ASTERISK IRIDIUM COMPLEXES; ARTIFICIAL PHOTOSYNTHESIS; AMMONIUM-NITRATE; SOLAR-ENERGY; EFFICIENT; LIGANDS; HETEROCYCLES; ACTIVATION; PALLADACYCLES; PHOSPHININES;

D O I：

10.1021/acs.organomet.5b00281

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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.

引用

页码：2943 / 2952

页数：10

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