Cyclometalated phosphinine-iridium(III) complexes: synthesis, reactivity, and application as phosphorus-containing water-oxidation catalysts

L.E.E. Broeckx, A. Bucci, C. Zuccaccia, M. Lutz, A. Macchioni, C. Müller

Research output: Contribution to journalArticleAcademicpeer-review

22 Citations (Scopus)

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).

Original languageEnglish
Pages (from-to)2943-2952
Number of pages10
JournalOrganometallics
Volume34
Issue number12
DOIs
Publication statusPublished - 22 Jun 2015

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Iridium
iridium
Phosphorus
phosphorus
reactivity
Cerium
catalysts
ammonium nitrates
Oxidation
oxidation
Catalysts
Stereoisomerism
Water
synthesis
cerium
water
Chlorides
chlorides
Nuclear magnetic resonance
Ligands

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Broeckx, L.E.E. ; Bucci, A. ; Zuccaccia, C. ; Lutz, M. ; Macchioni, A. ; Müller, C. / Cyclometalated phosphinine-iridium(III) complexes : synthesis, reactivity, and application as phosphorus-containing water-oxidation catalysts. In: Organometallics. 2015 ; Vol. 34, No. 12. pp. 2943-2952.
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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).",
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Cyclometalated phosphinine-iridium(III) complexes : synthesis, reactivity, and application as phosphorus-containing water-oxidation catalysts. / Broeckx, L.E.E.; Bucci, A.; Zuccaccia, C.; Lutz, M.; Macchioni, A.; Müller, C.

In: Organometallics, Vol. 34, No. 12, 22.06.2015, p. 2943-2952.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Cyclometalated phosphinine-iridium(III) complexes

T2 - synthesis, reactivity, and application as phosphorus-containing water-oxidation catalysts

AU - Broeckx, L.E.E.

AU - Bucci, A.

AU - Zuccaccia, C.

AU - Lutz, M.

AU - Macchioni, A.

AU - Müller, C.

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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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