Iron(II) Complexes Supported by a Tetradentate Ligand Providing a Strained Equatorial Coordination Environment: Geometric and Electronic‐Structural Implications

Schmidt, Steven J.; Kisslinger, Sandra; Würtele, Christian; Bonnet, Sylvestre; Schindler, Siegfried; Tuczek, Felix

doi:10.1002/zaac.201300425

Cited by 3 publications

(3 citation statements)

References 37 publications

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“…Metalation of L with Fe II (CF 3 SO 3 ) 2 ⋅ 4 MeCN yielded an orange crystalline compound [Fe II ( L )](H 2 O) 2 ](CF 3 SO 3 ) 2 ( 1 ), Figure . The crystal structure obtained is similar to an analogous [Fe II ( L )](SCN) 2 compound recently published . Thus, 1 has a distorted octahedral structure where the tetradentate L coordinates Fe II in the equatorial plane in a twisted planar configuration with Fe−N bond lengths of 2.213, 2.212, 2.216 and 2.199 Å ( r avg =2.21 Å).…”

Section: Resultssupporting

confidence: 71%

“…The crystal structure obtained is similar to an analogous [Fe II ( L )](SCN) 2 compound recently published. [8] Thus, 1 has a distorted octahedral structure where the tetradentate L coordinates Fe II in the equatorial plane in a twisted planar configuration with Fe–N bond lengths of 2.213, 2.212, 2.216 and 2.199 Å ( r avg = 2.21 Å). The aqua ligands are bonded to Fe II in the axial positions with Fe−O bond lengths of 2.109 and 2.096 Å.…”

Section: Resultsmentioning

confidence: 99%

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Hydrogen‐Atom Transfer Oxidation with H₂O₂ Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H₂O)₂]²⁺: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate

Khenkin

Madhu

Shimon

et al. 2017

Israel Journal of Chemistry

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The iron(II) triflate complex (1) of 1,2-bis(2,2′-bipyridyl-6-yl)ethane, with two bipyridine moieties connected by an ethane bridge, was prepared. Addition of aqueous 30% H2O2 to an acetonitrile solution of 1 yielded 2, a green compound with λmax=710 nm. Moessbauer measurements on 2 showed a doublet with an isomer shift (δ) of 0.35 mm/s and a quadrupole splitting (ΔEQ) of 0.86 mm/s, indicative of an antiferromagnetically coupled diferric complex. Resonance Raman spectra showed peaks at 883, 556 and 451 cm−1 that downshifted to 832, 540 and 441 cm−1 when 1 was treated with H218O2. All the spectroscopic data support the initial formation of a (μ-hydroxo)(μ-1,2-peroxo)diiron(III) complex that oxidizes carbon-hydrogen bonds. At 0°C 2 reacted with cyclohexene to yield allylic oxidation products but not epoxide. Weak benzylic C−H bonds of alkylarenes were also oxidized. A plot of the logarithms of the second order rate constants versus the bond dissociation energies of the cleaved C−H bond showed an excellent linear correlation. Along with the observation that oxidation of the probe substrate 2,2-dimethyl-1-phenylpropan-1-ol yielded the corresponding ketone but no benzaldehyde, and the kinetic isotope effect, kH/kD, of 2.8 found for the oxidation of xanthene, the results support the hypothesis for a metal-based H-atom abstraction mechanism. Complex 2 is a rare example of a (μ-hydroxo)(μ-1,2-peroxo)diiron(III) complex that can elicit the oxidation of carbon-hydrogen bonds.

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Section: Resultssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Hydrogen‐Atom Transfer Oxidation with H₂O₂ Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H₂O)₂]²⁺: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate

Khenkin

Madhu

Shimon

et al. 2017

Israel Journal of Chemistry

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“…A wide array of mono- and oligonuclear coordination compounds are known, ,− where the latter are usually accompanied by adventitious O 2– or bridging carboxylate anions (AcO – , PhCO 2 – ). It is evident that the flexibility of the ethylene spacer that separates bidentate subunits enhances the possibility of forming polymetallic architectures, consistent with multiple energy minima of equilibrated species.…”

Section: Architecture Of Qtpy Coordination Complexesmentioning

confidence: 99%

Quaterpyridines as Scaffolds for Functional Metallosupramolecular Materials

et al. 2016

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Quaterpyridine (qtpy) ligands have found significant applications as N-heterocyclic scaffolds in self-assembly processes, in particular the formation of various metallosupramolecular architectures, limited, however, by difficulties in their synthesis. Recent progress in the preparative organic and organometallic chemistry of polypyridines has resulted in the elimination of the most serious drawbacks concerning qtpy synthesis, consequently giving rise to a renewed interest in this class of compounds. Herein, we endeavor to define the essential aspects of quaterpyridine chemistry and provide the reader with a perspective on the ways in which this field has begun to flourish.

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High-spin enforcement in first-row metal complexes of a constrained polyaromatic ligand: synthesis, structure, and properties

et al. 2018

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Iron(II) Complexes Supported by a Tetradentate Ligand Providing a Strained Equatorial Coordination Environment: Geometric and Electronic‐Structural Implications

Cited by 3 publications

References 37 publications

Hydrogen‐Atom Transfer Oxidation with H₂O₂ Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H₂O)₂]²⁺: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate

Hydrogen‐Atom Transfer Oxidation with H₂O₂ Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H₂O)₂]²⁺: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate

Quaterpyridines as Scaffolds for Functional Metallosupramolecular Materials

High-spin enforcement in first-row metal complexes of a constrained polyaromatic ligand: synthesis, structure, and properties

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Iron(II) Complexes Supported by a Tetradentate Ligand Providing a Strained Equatorial Coordination Environment: Geometric and Electronic‐Structural Implications

Cited by 3 publications

References 37 publications

Hydrogen‐Atom Transfer Oxidation with H2O2 Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H2O)2]2+: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate

Hydrogen‐Atom Transfer Oxidation with H2O2 Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H2O)2]2+: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate

Quaterpyridines as Scaffolds for Functional Metallosupramolecular Materials

High-spin enforcement in first-row metal complexes of a constrained polyaromatic ligand: synthesis, structure, and properties

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Hydrogen‐Atom Transfer Oxidation with H₂O₂ Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H₂O)₂]²⁺: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate

Hydrogen‐Atom Transfer Oxidation with H₂O₂ Catalyzed by [FeII(1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane(H₂O)₂]²⁺: Likely Involvement of a (μ‐Hydroxo)(μ‐1,2‐peroxo)diiron(III) Intermediate