Chiral (1,2)‐Diphenylethylene‐Salen Complexes of Triel Metals: Coordination Patterns and Mechanistic Considerations in the Isoselective ROP of Lactide

Maudoux, Nicolas; Roisnel, Thierry; Dorcet, Vincent; Carpentier, Jean‐François; Sarazin, Yann

doi:10.1002/chem.201304788

Cited by 90 publications

(47 citation statements)

References 76 publications

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“…Furthermore, the ligand may provide the necessary conditions to sensitize the ion's photo‐ (or electro‐) luminescence . In this context, salen‐type ligands ( N , N '‐bis(salicylidine)diamine) have shown promising properties especially in binding late lanthanides and promoting Near‐IR luminescence of Yb 3+ complexes …”

Section: Methodsmentioning

confidence: 99%

Synthesis, Structural Characterization, and Chiroptical Studies of Bidentate Salen‐Type Lanthanide (III) Complexes

et al. 2015

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The salen-type ligand prepared with (R,R) diphenylethan-1,2-diamine and salicylaldehyde provides stable and inert complexes KLnL2 upon simple reaction with lanthanide halides or pseudohalides LnX3 (Ln = Tb(3+) -Lu(3+) ; X = Cl(-) or TfO(-) ) of its potassium salt. All the complexes were completely characterized through nuclear magnetic resonance (NMR), electronic circular dichroism (ECD) in the UV and some (Er(3+) , Tm(3+) , Yb(3+) ) also with Near-IR ECD (NIR-ECD) and luminescence (Tb(3+) , Tm(3+) ). Careful analysis of the NMR shifts demonstrated that the complexes are isostructural in solution and afforded an accurate geometry. This was further confirmed by means of Density Functional Theory (DFT) optimization of the Lu(3+) complex, and by comparing the ligand-centered experimental and time-dependent TD-DFT computed UV-ECD spectra. As final validation, we used the NIR-ECD spectrum of the Yb(3+) derivative calculated by means of Richardson's equations. The excellent match between calculated and experimental ECD spectra confirm the quality of the NMR structure.

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Section: Methodsmentioning

confidence: 99%

Synthesis, Structural Characterization, and Chiroptical Studies of Bidentate Salen‐Type Lanthanide (III) Complexes

et al. 2015

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“…Aryl propargylic ethers may undergo an intramolecular cyclization catalyzed by InI 3 (5 mol%) to produce 2H-chromenes (57). 85 In contrast to Au(I) catalysis, the In(III)-mediated process occurs with high regioselectivity with the formation of 6-endo-products.…”

Section: Intramolecular Hydroarylation Of Aryl Propargylic Ethers: Symentioning

confidence: 99%

Gallium and Indium Compounds in Homogeneous Catalysis

Dagorne

Fliedel

Frémont

2016

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The present contribution highlights the most recent and representative developments on the use of Ga and In species in homogeneous catalysis. Recent studies of various ligand‐supported Ga(III) and In(III) compounds in cyclic esters polymerization catalysis for the production of biodegradable polyester materials are also included. Various organic transformations may now be catalyzed using Ga(III) and In(III) Lewis acids allowing access to a wide range of valuable organic molecules through diverse reaction sequences. The recent use of stable and robust N ‐heterocyclic carbene Ga(III) and In(III) compounds as strong π‐Lewis acid catalysts for various organic reactions is also discussed: such species are certainly promising for the future developments of Ga(III)‐ and In(III)‐mediated reactions. Although Lewis acid‐assisted reactions certainly dominate the field in Ga(III) and In(III) chemistry, discrete low‐valent In(I) species, presently emerging in catalysis, clearly display a distinct reactivity allowing their exploitation both as soft Lewis acids and alkyl‐/allyl‐/arylating agents.

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“…In addition, the ring-opening copolymerization of epoxides and cyclic anhydrides has also the potential to produce a wider variety of polymer backbone structures [37,38]. Aluminum initiators were recognized as competent initiators employed for ROP of LA due to their effectiveness in controlling the tacticity of PLA [39][40][41][42][43][44][45][46]. Lots of endeavors have been dedicated to attain PLA with high stereotacticity.…”

Section: Introductionmentioning

confidence: 99%

Effect of the phenyl ring substituent on stereoselectivity in the ring-opening polymerization of the rac-lactide initiated by salen aluminum complexes

Wen

et al. 2015

Colloid Polym Sci

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A number of unreported salen aluminum complexes bearing Schiff base ligands starting from (R,R)-1,2-diammoniumcyclohexane mono-(+)-tartrate salt were synthesized. These complexes were characterized by 1 H, 13 C NMR, and elemental analysis. These complexes were employed as initiators for the ring-opening polymerization (ROP) of Llactide and rac-lactide. Complex 3 (R = Br) showed the highest activity for the ROP of L-lactide among these complexes, and complex 2 (R = i Pr) possessed the highest stereoselectivity for the ROP of rac-lactide among these aluminum isopropoxides. The kinetics studies of the polymerization employed complex 2 as initiator indicated that the polymerization rate was first-ordered in lactide and initiator.

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Chiral (1,2)‐Diphenylethylene‐Salen Complexes of Triel Metals: Coordination Patterns and Mechanistic Considerations in the Isoselective ROP of Lactide

Cited by 90 publications

References 76 publications

Synthesis, Structural Characterization, and Chiroptical Studies of Bidentate Salen‐Type Lanthanide (III) Complexes

Synthesis, Structural Characterization, and Chiroptical Studies of Bidentate Salen‐Type Lanthanide (III) Complexes

Gallium and Indium Compounds in Homogeneous Catalysis

Effect of the phenyl ring substituent on stereoselectivity in the ring-opening polymerization of the rac-lactide initiated by salen aluminum complexes

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