New ruthenium nitrosyl pincer complexes bearing an O2 Ligand. mono-oxygen transfer

Eran Fogler, Irena Efremenko, Moti Gargir, Gregory Leitus, Yael Diskin-Posner, Yehoshoa Ben-David, Jan M L Martin, David Milstein

Research output: Contribution to journalArticle

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Abstract

We report on Ru(II)2-O2) nitrosyl pincer complexes that can return to their original Ru(0) state by reaction with mono-oxygen scavengers. Potential intermediates were calculated by density functional theory (DFT) and a mechanism is proposed, revealing a new type of metal-ligand cooperation consisting of activation of the O2 moiety by both the metal center and the NO ligand. Reaction of the Ru(0) nitrosyl complex 1 with O2 quantitatively yielded the crystallographically characterized Ru(II)2-O2) nitrosyl complex 2. Reaction of 2 with the mono-oxygen scavengers phosphines or CO gave the Ru(0) complex 1 and phosphine oxides, or the carbonyl complex 3 (1 trapped by CO) and CO2, respectively. Reaction of 2 with 1 equiv of phosphine at room temperature or -40 °C resulted in immediate formation of half an equivalent of 1 and 1 equiv of phosphine oxide, while half an equivalent of 2 remained unchanged. Overnight reaction at room temperature of 2 with excess CO (≤3 equiv) resulted in 3 and CO2 gas as the only products. Reaction of 1 with 1 equiv of mono-oxygen source (dioxirane) at -78 °C yielded the Ru(II)2-O2) complex 2. Similarly, reaction of the Ru(0) dearomatized complex 4 with O2 led to the crystallographicaly characterized Ru(II)2-O2) complex 5. Further reaction of 5 with mono-oxygen scavengers (phosphines or CO) led to the Ru(0) complex 4 and phosphine oxides or complex 6 (4 trapped by CO) and CO2. When instead only 1 equiv of 5 was reacted with 1 equiv of phosphine at room temperature, immediate formation of half an equivalent of 4 and 1 equiv of phosphine oxide took place, while half an equivalent of 5 remained unchanged. When 5 reacted with an excess of CO (≤3 equiv), complex 6 and CO2 gas were the only products obtained. DFT studies indicate a new mode of metal-ligand cooperation involving the nitrosyl ligand in the oxygen transfer process.

Original languageEnglish
Pages (from-to)2253-2263
Number of pages11
JournalInorganic Chemistry
Volume54
Issue number5
DOIs
Publication statusPublished - Mar 2 2015

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phosphine
Bearings (structural)
Ruthenium
Carbon Monoxide
phosphines
ruthenium
Oxygen
Ligands
Oxides
ligands
oxygen
Phosphines
Metals
Density functional theory
oxides
Gases
room temperature
metals
density functional theory
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Fogler, E., Efremenko, I., Gargir, M., Leitus, G., Diskin-Posner, Y., Ben-David, Y., ... Milstein, D. (2015). New ruthenium nitrosyl pincer complexes bearing an O2 Ligand. mono-oxygen transfer. Inorganic Chemistry, 54(5), 2253-2263. https://doi.org/10.1021/ic502832j

New ruthenium nitrosyl pincer complexes bearing an O2 Ligand. mono-oxygen transfer. / Fogler, Eran; Efremenko, Irena; Gargir, Moti; Leitus, Gregory; Diskin-Posner, Yael; Ben-David, Yehoshoa; Martin, Jan M L; Milstein, David.

In: Inorganic Chemistry, Vol. 54, No. 5, 02.03.2015, p. 2253-2263.

Research output: Contribution to journalArticle

Fogler, E, Efremenko, I, Gargir, M, Leitus, G, Diskin-Posner, Y, Ben-David, Y, Martin, JML & Milstein, D 2015, 'New ruthenium nitrosyl pincer complexes bearing an O2 Ligand. mono-oxygen transfer', Inorganic Chemistry, vol. 54, no. 5, pp. 2253-2263. https://doi.org/10.1021/ic502832j
Fogler E, Efremenko I, Gargir M, Leitus G, Diskin-Posner Y, Ben-David Y et al. New ruthenium nitrosyl pincer complexes bearing an O2 Ligand. mono-oxygen transfer. Inorganic Chemistry. 2015 Mar 2;54(5):2253-2263. https://doi.org/10.1021/ic502832j
Fogler, Eran ; Efremenko, Irena ; Gargir, Moti ; Leitus, Gregory ; Diskin-Posner, Yael ; Ben-David, Yehoshoa ; Martin, Jan M L ; Milstein, David. / New ruthenium nitrosyl pincer complexes bearing an O2 Ligand. mono-oxygen transfer. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 5. pp. 2253-2263.
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abstract = "We report on Ru(II)(μ2-O2) nitrosyl pincer complexes that can return to their original Ru(0) state by reaction with mono-oxygen scavengers. Potential intermediates were calculated by density functional theory (DFT) and a mechanism is proposed, revealing a new type of metal-ligand cooperation consisting of activation of the O2 moiety by both the metal center and the NO ligand. Reaction of the Ru(0) nitrosyl complex 1 with O2 quantitatively yielded the crystallographically characterized Ru(II) (μ2-O2) nitrosyl complex 2. Reaction of 2 with the mono-oxygen scavengers phosphines or CO gave the Ru(0) complex 1 and phosphine oxides, or the carbonyl complex 3 (1 trapped by CO) and CO2, respectively. Reaction of 2 with 1 equiv of phosphine at room temperature or -40 °C resulted in immediate formation of half an equivalent of 1 and 1 equiv of phosphine oxide, while half an equivalent of 2 remained unchanged. Overnight reaction at room temperature of 2 with excess CO (≤3 equiv) resulted in 3 and CO2 gas as the only products. Reaction of 1 with 1 equiv of mono-oxygen source (dioxirane) at -78 °C yielded the Ru(II)(μ2-O2) complex 2. Similarly, reaction of the Ru(0) dearomatized complex 4 with O2 led to the crystallographicaly characterized Ru(II)(μ2-O2) complex 5. Further reaction of 5 with mono-oxygen scavengers (phosphines or CO) led to the Ru(0) complex 4 and phosphine oxides or complex 6 (4 trapped by CO) and CO2. When instead only 1 equiv of 5 was reacted with 1 equiv of phosphine at room temperature, immediate formation of half an equivalent of 4 and 1 equiv of phosphine oxide took place, while half an equivalent of 5 remained unchanged. When 5 reacted with an excess of CO (≤3 equiv), complex 6 and CO2 gas were the only products obtained. DFT studies indicate a new mode of metal-ligand cooperation involving the nitrosyl ligand in the oxygen transfer process.",
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AU - Leitus, Gregory

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N2 - We report on Ru(II)(μ2-O2) nitrosyl pincer complexes that can return to their original Ru(0) state by reaction with mono-oxygen scavengers. Potential intermediates were calculated by density functional theory (DFT) and a mechanism is proposed, revealing a new type of metal-ligand cooperation consisting of activation of the O2 moiety by both the metal center and the NO ligand. Reaction of the Ru(0) nitrosyl complex 1 with O2 quantitatively yielded the crystallographically characterized Ru(II) (μ2-O2) nitrosyl complex 2. Reaction of 2 with the mono-oxygen scavengers phosphines or CO gave the Ru(0) complex 1 and phosphine oxides, or the carbonyl complex 3 (1 trapped by CO) and CO2, respectively. Reaction of 2 with 1 equiv of phosphine at room temperature or -40 °C resulted in immediate formation of half an equivalent of 1 and 1 equiv of phosphine oxide, while half an equivalent of 2 remained unchanged. Overnight reaction at room temperature of 2 with excess CO (≤3 equiv) resulted in 3 and CO2 gas as the only products. Reaction of 1 with 1 equiv of mono-oxygen source (dioxirane) at -78 °C yielded the Ru(II)(μ2-O2) complex 2. Similarly, reaction of the Ru(0) dearomatized complex 4 with O2 led to the crystallographicaly characterized Ru(II)(μ2-O2) complex 5. Further reaction of 5 with mono-oxygen scavengers (phosphines or CO) led to the Ru(0) complex 4 and phosphine oxides or complex 6 (4 trapped by CO) and CO2. When instead only 1 equiv of 5 was reacted with 1 equiv of phosphine at room temperature, immediate formation of half an equivalent of 4 and 1 equiv of phosphine oxide took place, while half an equivalent of 5 remained unchanged. When 5 reacted with an excess of CO (≤3 equiv), complex 6 and CO2 gas were the only products obtained. DFT studies indicate a new mode of metal-ligand cooperation involving the nitrosyl ligand in the oxygen transfer process.

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