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

Leen E E Broeckx; Alberto Bucci; Cristiano Zuccaccia; Martin Lutz; Alceo Macchioni; Christian Müller

doi:10.1021/acs.organomet.5b00281

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

Leen E E Broeckx, Alberto Bucci, Cristiano Zuccaccia, Martin Lutz, Alceo Macchioni^*, Christian Müller

^*Corresponding author for this work

Sub Crystal and Structural Chemistry

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The novel phosphinine-based coordination compound [Cp∗Ir(P^C)(CH<inf>3</inf>CN)]CF<inf>3</inf>SO<inf>3</inf> (P^C = cyclometalated 2,4,6-triphenylphosphinine) could be synthesized by chloride abstraction from [Cp∗Ir(P^C)Cl] with AgOSO<inf>2</inf>CF<inf>3</inf> 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(P^C)] species, possibly OH-functionalized but still having Cp∗ and P^C-ligands contemporary bound to iridium, are present in solution, even under catalytic conditions. (Figure Presented).

Original language	English
Pages (from-to)	2943-2952
Number of pages	10
Journal	Organometallics
Volume	34
Issue number	12
DOIs	https://doi.org/10.1021/acs.organomet.5b00281
Publication status	Published - 22 Jun 2015

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@article{4a6ecad359a04870a0aa3543189f0023,

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

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

author = "Broeckx, {Leen E E} and Alberto Bucci and Cristiano Zuccaccia and Martin Lutz and Alceo Macchioni and Christian M{\"u}ller",

year = "2015",

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doi = "10.1021/acs.organomet.5b00281",

language = "English",

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T1 - Cyclometalated Phosphinine-Iridium(III) Complexes

T2 - Synthesis, Reactivity, and Application as Phosphorus-Containing Water-Oxidation Catalysts

AU - Broeckx, Leen E E

AU - Bucci, Alberto

AU - Zuccaccia, Cristiano

AU - Lutz, Martin

AU - Macchioni, Alceo

AU - Müller, Christian

PY - 2015/6/22

Y1 - 2015/6/22

N2 - The novel phosphinine-based coordination compound [Cp∗Ir(P^C)(CH3CN)]CF3SO3 (P^C = cyclometalated 2,4,6-triphenylphosphinine) could be synthesized by chloride abstraction from [Cp∗Ir(P^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=C double bonds with formation of four stereoisomers. Moreover, [Cp∗Ir(P^C)] species, possibly OH-functionalized but still having Cp∗ and P^C-ligands contemporary bound to iridium, are present in solution, even under catalytic conditions. (Figure Presented).

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

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ER -

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

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