Planar Chiral Iridium Complexes with the Δ‐TRISPHAT Anion: Toward the First Enantiopure <i>o</i>‐Quinone Methide π‐Complex

Moussa, Jamal; Chamoreau, Lise Marie; Amouri, Hani

doi:10.1002/chir.22183

Cited by 10 publications

(4 citation statements)

References 46 publications

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“…The enantiopurities of the thioether complexes were measured by 1 H NMR spectra, because the Δ and Λ isomers have different chemical shifts when S -binol was added . As shown in Figure , the resonance peak at 8.84 ppm in rac- 1 , assigned to the H 6 of bpy, is split into 8.81 and 8.73 ppm when 40 equiv of S -binol was added.…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Syntheses of Sulfoxides in Octahedral Ruthenium(II) Complexes via a Chiral-at-Metal Strategy

Wen

Yao

et al. 2015

Inorg. Chem.

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The preparation of chiral 2-(alkylsulfinyl)phenol compounds by enantioselective coordination-oxidation of the thioether ruthenium complexes with a chiral-at-metal strategy has been developed. The enantiomerically pure sulfoxide complexes Δ-[Ru(bpy)2{(R)-LO-R}](PF6) (bpy is 2,2'-bipyridine, HLO-R is 2-(alkylsulfinyl)phenol, R = Me (Δ-1a), Et (Δ-2a), iPr (Δ-3a), Bn (Δ-4a), and Nap (Δ-5a)) and Λ-[Ru(bpy)2{(S)-LO-R}](PF6) (R = Me (Λ-1a), Et (Λ-2a), iPr (Λ-3a), Bn (Λ-4a), and Nap (Λ-5a)) have been synthesized by the reaction of Δ-[Ru(bpy)2(py)2](2+) or Λ-[Ru(bpy)2(py)2](2+) with the prochiral thioether ligands 2-(alkylthio)phenol (HL-R), followed by enantioselective oxidation with m-CPBA as oxidant. The X-ray crystallography was used to verify the stereochemistry of ruthenium complexes and sulfur atoms. The configurations of the ruthenium complexes are stable during the coordination and oxidation reactions. Moreover, the chiral sulfoxide ligands are enantioselectively generated by controlling of the configuration of ruthenium centers in the course of oxidation reaction. That is, the Λ configuration at the ruthenium center generates the S sulfoxide ligand; on the contrary, the Δ configuration of the ruthenium complex originates the R sulfoxide ligand. Acidolysis of Λ-[Ru(bpy)2{(R)-LO-R}](PF6) and Δ-[Ru(bpy)2{(S)-LO-R}](PF6) complexes in the presence of TFA-MeCN afforded the chiral ligands (R)-HLO-R and (S)-HLO-R in 96-99% ee values, respectively. Importantly, the chiral ruthenium complexes can be recycled as Δ/Λ-[Ru(bpy)2(MeCN)2](PF6)2 and reused in a next reaction cycle with complete retention of the configurations at ruthenium centers.

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Section: Resultsmentioning

confidence: 99%

Enantioselective Syntheses of Sulfoxides in Octahedral Ruthenium(II) Complexes via a Chiral-at-Metal Strategy

Wen

Yao

et al. 2015

Inorg. Chem.

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“…To achieve our objectives we sought the design of chiral organometallic ligands with rigid frameworks displaying central and planar chirality (Figure ) . The goal is to place the Pt(terpy) luminophore in a chiral environment and force the well‐defined assembly to adopt a homochiral or a heterochiral arrangement at the supramolecular level.…”

Section: Figurementioning

confidence: 99%

“…[18][19][20][21][22] To achieve our objectives we sought the design of chiral organometallic ligands [23] with rigid frameworks displaying central and planar chirality ( Figure 1). [24,25] The goal is to place the Pt(terpy) luminophorei nachirale nvironmenta nd force the well-defined assembly to adopt ah omochiralo raheterochiral arrangement at the supramolecular level. More interestingly, we anticipated that the photoluminescent properties of these arrangements might be influencedb yt he morphologya nd molecular arrays of the aggregates.…”

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confidence: 99%

Highly Phosphorescent Crystals of Square‐Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements, Induced Circular Dichroism, and TD‐DFT Calculations

Sesolis

Dubarle‐Offner

Chan

et al. 2016

Chemistry A European J

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A novel class of chiral luminescent square-planar platinum complexes with a π-bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls the aggregation of this square planar luminophor and imposes a homo- or hetero-chiral arrangement at the supramolecular level, displaying non-covalent Pt-Pt and π-π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD-DFT calculation is obtained to rationalize this unique behavior.

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“…For instance, octahedral iridium complexes displaying helical chirality (∆, Λ) show a stable configuration at the metal center [15][16][17][18][19]. Coordination and organometallic complexes with planar chirality also show stable configuration [20][21][22][23][24][25]. In contrast, half-sandwich rhodium and iridium complexes with piano stool geometry, displaying central chirality are labile in solution, as demonstrated by Brunner and co-workers and others [26][27][28][29].…”

Section: Introductionmentioning

confidence: 99%

Enantiopure Cyclometalated Rh(III) and Ir(III) Complexes Displaying Rigid Configuration at Metal Center: Design, Structures, Chiroptical Properties and Role of the Iodide Ligand

et al. 2022

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Enantiopure N-heterocyclic carbene half-sandwich metal complexes of the general formula [Cp*M(C^C:)I] (M = Rh, Ir; C^C: = NI-NHC; NI-H = Naphthalimide; NHC = N-heterocyclic carbene) are reported. The rhodium compound was obtained as a single isomer displaying six membered metallacycle and was resolved on chiral column chromatography to the corresponding enantiomers (S)-[Cp*Rh(C^C:)I] (S)-2 and (R)-[Cp*Rh(C^C:)I] (R)-2. The iridium congener, however, furnishes a pair of regioisomers, which were resolved into (S)-[Cp*Ir(C^C:)I] (S)-3 and (R)-[Cp*Ir(C^C:)I] (R)-3 and (S)-[Cp*Ir(C^C:)I] (S)-4 and (R)-[Cp*Ir(C^C:)I] (R)-4. These regioisomers differ from each other, only by the size of the metallacycle; five-membered for 3 and six-membered for 4. The molecular structures of (S)-2 and (S)-4 are reported. Moreover, the chiroptical properties of these compounds are presented and discussed. These compounds display exceptional stable configurations at the metal center in solution with enantiomerization barrier ΔG≠ up to 124 kJ/mol. This is because the nature of the naphthalimide-NHC clamp ligand and the iodide ligand contribute to their configuration’s robustness. In contrast to related complexes reported in the literature, which are often labile in solution.

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Planar Chiral Iridium Complexes with the Δ‐TRISPHAT Anion: Toward the First Enantiopure o‐Quinone Methide π‐Complex

Cited by 10 publications

References 46 publications

Enantioselective Syntheses of Sulfoxides in Octahedral Ruthenium(II) Complexes via a Chiral-at-Metal Strategy

Enantioselective Syntheses of Sulfoxides in Octahedral Ruthenium(II) Complexes via a Chiral-at-Metal Strategy

Highly Phosphorescent Crystals of Square‐Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements, Induced Circular Dichroism, and TD‐DFT Calculations

Enantiopure Cyclometalated Rh(III) and Ir(III) Complexes Displaying Rigid Configuration at Metal Center: Design, Structures, Chiroptical Properties and Role of the Iodide Ligand

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