Trifluoromethanesulfonate (triflate) as a moderately coordinating anion

Studies from chemistry of the cationic coordinatively unsaturated mono- and diruthenium amidinates

Taizo Hayashida, Hideo Kondo, Jun ichi Terasawa, Karl Kirchner, Yusuke Sunada, Hideo Nagashima

Research output: Contribution to journalArticle

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Abstract

Triflate complexes of mono- and diruthenium amidinates, (η6-C6R6)Ru(κ1-OTf){η2-R′N{double bond, long}C(R′′)NR′} (1: R = Me; 2: R = H) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5R5) (3: R = Me; 4: R = H), are synthesized, and coordination behavior of the triflate anion to the coordinatively unsaturated ruthenium species is investigated by crystallography and variable temperature (VT) NMR spectroscopy (19F, 1H). The monoruthenium amidinate complexes have three-legged piano-stool structures in single crystals, which include a κ1-OTf ligand with the Ru-O bond of 2.15-2.20 Å. In contrast, reversible dissociation of OTf is observed in variable temperature 1H NMR spectroscopy in liquid states; the activation energy for the dissociation and recombination of the OTf ligand is varied with the substituents on the arene and amidinate ligand in the corresponding ruthenium cation and the solvent used. A typical example of moderately coordinating ability of the OTf ligand is seen in 19F NMR spectra of (η6-C6Me6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (1a) and (η6-C6H6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (2a) in CD2Cl2 at the temperature range from -90 to 20 °C, in which the OTf anion is dissociated in 1a, whereas 2a has a relatively robust Ru-OTf bond. Combination of crystallography and VT NMR contributes to understanding the difference in coordination behavior of the OTf ligand between two diruthenium amidinates, (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5Me5) (3) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5H5) (4); the results suggest that the electron-donating and sterically demanding η5-C5Me5 helps for dissociation of the triflate ligand. Moderate coordinating ability of the triflate anion sometimes provides characteristic reactions of mono- and diruthenium amidinates which differ from the corresponding neutral halogeno-compounds or cationic coordinatively unsaturated homologues bearing fluorinated tetraarylborates; a typical example is given by inhibition of coordination of ethylene to the [(η6-C6H6)Ru{η2-tBuN{double bond, long}C(Ph)NtBu}]+ species by the OTf ligand.

Original languageEnglish
Pages (from-to)382-394
Number of pages13
JournalJournal of Organometallic Chemistry
Volume692
Issue number1-3
DOIs
Publication statusPublished - Jan 1 2007

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Anions
Negative ions
Ligands
chemistry
anions
ligands
nuclear magnetic resonance
Crystallography
Temperature
Ruthenium
dissociation
Nuclear magnetic resonance spectroscopy
ruthenium
crystallography
Bearings (structural)
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
temperature
trifluoromethanesulfonic acid
spectroscopy

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Trifluoromethanesulfonate (triflate) as a moderately coordinating anion : Studies from chemistry of the cationic coordinatively unsaturated mono- and diruthenium amidinates. / Hayashida, Taizo; Kondo, Hideo; Terasawa, Jun ichi; Kirchner, Karl; Sunada, Yusuke; Nagashima, Hideo.

In: Journal of Organometallic Chemistry, Vol. 692, No. 1-3, 01.01.2007, p. 382-394.

Research output: Contribution to journalArticle

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abstract = "Triflate complexes of mono- and diruthenium amidinates, (η6-C6R6)Ru(κ1-OTf){η2-R′N{double bond, long}C(R′′)NR′} (1: R = Me; 2: R = H) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5R5) (3: R = Me; 4: R = H), are synthesized, and coordination behavior of the triflate anion to the coordinatively unsaturated ruthenium species is investigated by crystallography and variable temperature (VT) NMR spectroscopy (19F, 1H). The monoruthenium amidinate complexes have three-legged piano-stool structures in single crystals, which include a κ1-OTf ligand with the Ru-O bond of 2.15-2.20 {\AA}. In contrast, reversible dissociation of OTf is observed in variable temperature 1H NMR spectroscopy in liquid states; the activation energy for the dissociation and recombination of the OTf ligand is varied with the substituents on the arene and amidinate ligand in the corresponding ruthenium cation and the solvent used. A typical example of moderately coordinating ability of the OTf ligand is seen in 19F NMR spectra of (η6-C6Me6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (1a) and (η6-C6H6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (2a) in CD2Cl2 at the temperature range from -90 to 20 °C, in which the OTf anion is dissociated in 1a, whereas 2a has a relatively robust Ru-OTf bond. Combination of crystallography and VT NMR contributes to understanding the difference in coordination behavior of the OTf ligand between two diruthenium amidinates, (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5Me5) (3) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5H5) (4); the results suggest that the electron-donating and sterically demanding η5-C5Me5 helps for dissociation of the triflate ligand. Moderate coordinating ability of the triflate anion sometimes provides characteristic reactions of mono- and diruthenium amidinates which differ from the corresponding neutral halogeno-compounds or cationic coordinatively unsaturated homologues bearing fluorinated tetraarylborates; a typical example is given by inhibition of coordination of ethylene to the [(η6-C6H6)Ru{η2-tBuN{double bond, long}C(Ph)NtBu}]+ species by the OTf ligand.",
author = "Taizo Hayashida and Hideo Kondo and Terasawa, {Jun ichi} and Karl Kirchner and Yusuke Sunada and Hideo Nagashima",
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T1 - Trifluoromethanesulfonate (triflate) as a moderately coordinating anion

T2 - Studies from chemistry of the cationic coordinatively unsaturated mono- and diruthenium amidinates

AU - Hayashida, Taizo

AU - Kondo, Hideo

AU - Terasawa, Jun ichi

AU - Kirchner, Karl

AU - Sunada, Yusuke

AU - Nagashima, Hideo

PY - 2007/1/1

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N2 - Triflate complexes of mono- and diruthenium amidinates, (η6-C6R6)Ru(κ1-OTf){η2-R′N{double bond, long}C(R′′)NR′} (1: R = Me; 2: R = H) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5R5) (3: R = Me; 4: R = H), are synthesized, and coordination behavior of the triflate anion to the coordinatively unsaturated ruthenium species is investigated by crystallography and variable temperature (VT) NMR spectroscopy (19F, 1H). The monoruthenium amidinate complexes have three-legged piano-stool structures in single crystals, which include a κ1-OTf ligand with the Ru-O bond of 2.15-2.20 Å. In contrast, reversible dissociation of OTf is observed in variable temperature 1H NMR spectroscopy in liquid states; the activation energy for the dissociation and recombination of the OTf ligand is varied with the substituents on the arene and amidinate ligand in the corresponding ruthenium cation and the solvent used. A typical example of moderately coordinating ability of the OTf ligand is seen in 19F NMR spectra of (η6-C6Me6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (1a) and (η6-C6H6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (2a) in CD2Cl2 at the temperature range from -90 to 20 °C, in which the OTf anion is dissociated in 1a, whereas 2a has a relatively robust Ru-OTf bond. Combination of crystallography and VT NMR contributes to understanding the difference in coordination behavior of the OTf ligand between two diruthenium amidinates, (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5Me5) (3) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5H5) (4); the results suggest that the electron-donating and sterically demanding η5-C5Me5 helps for dissociation of the triflate ligand. Moderate coordinating ability of the triflate anion sometimes provides characteristic reactions of mono- and diruthenium amidinates which differ from the corresponding neutral halogeno-compounds or cationic coordinatively unsaturated homologues bearing fluorinated tetraarylborates; a typical example is given by inhibition of coordination of ethylene to the [(η6-C6H6)Ru{η2-tBuN{double bond, long}C(Ph)NtBu}]+ species by the OTf ligand.

AB - Triflate complexes of mono- and diruthenium amidinates, (η6-C6R6)Ru(κ1-OTf){η2-R′N{double bond, long}C(R′′)NR′} (1: R = Me; 2: R = H) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5R5) (3: R = Me; 4: R = H), are synthesized, and coordination behavior of the triflate anion to the coordinatively unsaturated ruthenium species is investigated by crystallography and variable temperature (VT) NMR spectroscopy (19F, 1H). The monoruthenium amidinate complexes have three-legged piano-stool structures in single crystals, which include a κ1-OTf ligand with the Ru-O bond of 2.15-2.20 Å. In contrast, reversible dissociation of OTf is observed in variable temperature 1H NMR spectroscopy in liquid states; the activation energy for the dissociation and recombination of the OTf ligand is varied with the substituents on the arene and amidinate ligand in the corresponding ruthenium cation and the solvent used. A typical example of moderately coordinating ability of the OTf ligand is seen in 19F NMR spectra of (η6-C6Me6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (1a) and (η6-C6H6)Ru(κ1-OTf){η2-iPrN{double bond, long}C(Me)NiPr} (2a) in CD2Cl2 at the temperature range from -90 to 20 °C, in which the OTf anion is dissociated in 1a, whereas 2a has a relatively robust Ru-OTf bond. Combination of crystallography and VT NMR contributes to understanding the difference in coordination behavior of the OTf ligand between two diruthenium amidinates, (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5Me5) (3) and (η5-C5Me5)Ru(μ-η2-iPrN{double bond, long}C(Me)NiPr)Ru(κ1-OTf)(η5-C5H5) (4); the results suggest that the electron-donating and sterically demanding η5-C5Me5 helps for dissociation of the triflate ligand. Moderate coordinating ability of the triflate anion sometimes provides characteristic reactions of mono- and diruthenium amidinates which differ from the corresponding neutral halogeno-compounds or cationic coordinatively unsaturated homologues bearing fluorinated tetraarylborates; a typical example is given by inhibition of coordination of ethylene to the [(η6-C6H6)Ru{η2-tBuN{double bond, long}C(Ph)NtBu}]+ species by the OTf ligand.

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