Cationic metal nitrosyl complexes. 6. Characterization of the 19-electron iron nitrosyl radical cation [Fe(NO)2LL'2]+

Ballivet‐Tkatchenko, Danielle; Nickel, B.; Rassat, A.; Vincent-Vaucquelin, J.

doi:10.1021/ic00239a034

Cited by 13 publications

(2 citation statements)

References 2 publications

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“…The thus does not give any signal in the X-band EPR spectrum. [69] Conversely, the X-band EPR spectrum of 1 (Figure 1) indicates the presence of one main iron-nitrosyl species in solution. The signal at g value 2.01 could be assigned to the iron-nitrosyl complex.…”

Section: Characterization Of Iron-containing Ionic Liquid [Bmim][fe(no)2cl2]mentioning

confidence: 97%

“…[72][73][74] The FT-IR spectrum of the complex precursor [Fe(NO)2(µ-Cl)]2 showed two intense bands at 1722 and 1822 cm -1 belonging to the NO stretching absorption (Figure S3, Supporting Information). [69] Such stretching bands were visible, although slightly shifted (1700 and 1779 cm -1 ), in the FT-IR spectrum of 1 (Figure S3, Supporting Information), indicating the presence of NO fragments in the Fe-containing ionic liquid. These IR frequencies are comparable to those reported for (Et4N)[FeCl2(NO)2] (1765 and 1692 cm -1 ), thus suggesting that similar DNIC {[Fe(NO)2Cl2] -} species are present in both complexes.…”

Section: Characterization Of Iron-containing Ionic Liquid [Bmim][fe(no)2cl2]mentioning

confidence: 99%

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On the real catalytically active species for CO2 fixation into cyclic carbonates under near ambient conditions: Dissociation equilibrium of [BMIm][Fe(NO)2Cl2] dependant on reaction temperature

Leu

Vicente

Fernandes

et al. 2019

Applied Catalysis B: Environmental

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An imidazolium based iron-containing ionic liquid [BMIm][Fe(NO)2Cl2] (BMIm = 1n-butyl-3-methyl-imidazolium) has been synthesized for the first time and fully characterized employing a wide range of techniques. The iron-based containing ionic liquid was found to be an active catalyst for the cycloaddition of CO2 to epoxides, giving high conversions for various substrates under near ambient conditions. In addition, the catalytic system showed a good recycling performance for five consecutive reaction cycles. Key mechanistic studies demonstrated that a bifunctional catalytic system is generated in situ by the partial dissociation of the iron-based ionic liquid into [BMIm][Cl], which results in a very efficient catalyst without the need of any additive or co-catalyst. The metal center plays a role as Lewis acid and activate the epoxide group, and the chloride anion, as part of [BMIm][Cl] moiety, acts as nucleophile and leads to the ring opening through a nucleophilic attack on the less sterically-hindered Che process is favoured by an interaction via H-bonding between the substrate and the H-C2 of the imidazolium ring, as was demonstrated by additional experiments. Kinetic studies indicated that the process followed first-order kinetics with respect to epoxide concentration and proved the existence of a reversible coordination/de-coordination equilibrium in which the active species are generated from the [BMIm][Fe(NO)2Cl2] complex.

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Section: Characterization Of Iron-containing Ionic Liquid [Bmim][fe(no)2cl2]mentioning

confidence: 97%

Section: Characterization Of Iron-containing Ionic Liquid [Bmim][fe(no)2cl2]mentioning

confidence: 99%

On the real catalytically active species for CO2 fixation into cyclic carbonates under near ambient conditions: Dissociation equilibrium of [BMIm][Fe(NO)2Cl2] dependant on reaction temperature

Leu

Vicente

Fernandes

et al. 2019

Applied Catalysis B: Environmental

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Mechanistic Aspects of Organometallic Radical Reactions

Tyler

1988

Progress in Inorganic Chemistry

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ChemInform Abstract: Catonic Metal Nitrosyl Complexes. Part 6. Characterization of the 19‐Electron Radical Cation (Fe(NO)2LL′2)+.

Ballivet‐Tkatchenko¹,

Nickel

Rassat

et al. 1987

ChemInform

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Cationic metal nitrosyl complexes. 6. Characterization of the 19-electron iron nitrosyl radical cation [Fe(NO)2LL'2]+

Cited by 13 publications

References 2 publications

On the real catalytically active species for CO2 fixation into cyclic carbonates under near ambient conditions: Dissociation equilibrium of [BMIm][Fe(NO)2Cl2] dependant on reaction temperature

On the real catalytically active species for CO2 fixation into cyclic carbonates under near ambient conditions: Dissociation equilibrium of [BMIm][Fe(NO)2Cl2] dependant on reaction temperature

Mechanistic Aspects of Organometallic Radical Reactions

ChemInform Abstract: Catonic Metal Nitrosyl Complexes. Part 6. Characterization of the 19‐Electron Radical Cation (Fe(NO)2LL′2)+.

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