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Resolution, structures, and vibrational circular dichroism of helicoidal trinickel and tricobalt paddlewheel complexes

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorCORTIJO, Miguel
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorVALENTÍN-PÉREZ, Ángela
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorROSA, Patrick
hal.structure.identifierInstitut des Sciences Moléculaires [ISM]
dc.contributor.authorDAUGEY, Nicolas
hal.structure.identifierInstitut des Sciences Moléculaires [ISM]
dc.contributor.authorBUFFETEAU, Thierry
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorHILLARD, Elizabeth
dc.date.issued2020-06
dc.identifier.issn0899-0042
dc.description.abstractEnIt has been recently shown that enantiomers of the helicoidal paddlewheel complex [Co3(dpa)4(CH3CN)2]2+ (dpa = the anion of 2,2′‐dipyridylamine) can be resolved using the chiral [As2(tartrate)2]2− anion (AsT) and that these complexes demonstrate a strong chiroptical response in the ultraviolet‐visible and X‐ray energy regions. Here we report that the nickel congener, [Ni3(dpa)4(CH3CN)2]2+, can likewise be resolved using AsT. Depending on the stereochemistry of the enantiopure AsT anion, one or the other of the trinickel enantiomers crystallize from CH3CN and diethyl ether in space group P4212 as the (NBu4)2[Ni3(dpa)4(CH3CN)2](AsT)2·[solvent] salt. After resolution, the AsT salts were converted into the PF6− salts by anion exchange, with retention of the chirality of the trinickel complex. The enantiopure [Ni3(dpa)4(CH3CN)2](PF6)2·2CH3CN and [Co3(dpa)4(CH3CN)2](PF6)2·CH3CN·C4H10O compounds crystallize in space groups C2 and P21, respectively. Both the Ni(II) and Co(II) complex cations are stable towards racemization in CH3CN. Vibrational circular dichroism (VCD) data obtained in CD3CN demonstrate the expected mirror image spectra for the enantiomers, the observed peaks arising from the dpa ligand. The VCD response is significant, with Δε values up to 6 Lmol−1 cm−1 and vibrational dissymmetry factors on the order of 10−3. Density functional theory calculations well reproduce the experimental spectra, showing little difference between the peak position, sign, and intensity in the VCD for the cobalt and nickel complexes. These results suggest that VCD enhancement of these peaks is unlikely, and their remarkable intensity may be due to their rigid helicoidal structure.
dc.language.isoen
dc.publisherWiley
dc.subject.enpaddlewheel complexes
dc.subject.enhelicoidal chirality
dc.subject.enarsenyl tartrate
dc.subject.enchiral resolution
dc.subject.enX-ray crystallography
dc.subject.envibrational circular dichroism
dc.title.enResolution, structures, and vibrational circular dichroism of helicoidal trinickel and tricobalt paddlewheel complexes
dc.typeArticle de revue
dc.identifier.doi10.1002/chir.23211
dc.subject.halChimie/Matériaux
bordeaux.journalChirality
bordeaux.page753-764
bordeaux.volume32
bordeaux.issue6
bordeaux.peerReviewedoui
hal.identifierhal-02613849
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-02613849v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chirality&rft.date=2020-06&rft.volume=32&rft.issue=6&rft.spage=753-764&rft.epage=753-764&rft.eissn=0899-0042&rft.issn=0899-0042&rft.au=CORTIJO,%20Miguel&VALENT%C3%8DN-P%C3%89REZ,%20%C3%81ngela&ROSA,%20Patrick&DAUGEY,%20Nicolas&BUFFETEAU,%20Thierry&rft.genre=article


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