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

11 Citations (Scopus)

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

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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    Fogler, E., Efremenko, I., Gargir, M., Leitus, G., Diskin-Posner, Y., Ben-David, Y., Martin, J. M. L., & 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