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Nickel(II) Complexes with Electron-Rich, Sterically Hindered PNP Pincer Ligands Enable Uncommon Modes of Ligand Dearomatization
https://oist.repo.nii.ac.jp/records/1309
https://oist.repo.nii.ac.jp/records/130954df9864-aea1-4600-a45a-c0d8013c9dd6
名前 / ファイル | ライセンス | アクション |
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Manuscript20191009_revised (1.5 MB)
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2020-03-19 | |||||
タイトル | ||||||
言語 | en | |||||
タイトル | Nickel(II) Complexes with Electron-Rich, Sterically Hindered PNP Pincer Ligands Enable Uncommon Modes of Ligand Dearomatization | |||||
言語 | ||||||
言語 | eng | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
資源タイプ | journal article | |||||
著者(英) |
Lapointe, Sébastien
× Lapointe, Sébastien× Khaskin, Eugene× Fayzullin, Robert R.× Khusnutdinova, Julia R. |
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書誌情報 |
en : Organometallics 巻 38, 号 22, p. 4433-4447, 発行日 2019-11-01 |
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抄録 | ||||||
内容記述タイプ | Other | |||||
内容記述 | We report the reactivity and characterization of hydride, methyl, and bromo Ni-II complexes with a new class of electron-rich and sterically hindered PNP pincer ligands, Me₄PNPR (R = Pr-i, Bu-t), in which a classical metal-ligand cooperative mode of reactivity via CH2 arm deprotonation is blocked by methylation. This enables new, uncommon modes of PNP ligand dearomatization that involve reactivity in the para position of the pyridine ring. In particular, the reduction of [(Me₄PNPiPr) (NiMe)-Me-II]B(Ar-F)(4) with KC₈ leads to the formation of a new C-C bond via dimerization of two complexes through the para position. This reactivity stands in sharp contrast to the previously reported bromo or chloro complexes, where stable Ni-I halogen moieties are formed. Computational analysis showed a greater propensity for ligand-centered radical formation for the presumed intermediate one-electron-reduced species. UV-induced homolysis of the Ni-II-Me bond in [(Me₄PNPiPr) (NiMe)-Me-II]B(Ar-F)(4) leads to the formation of a Me radical detected by radical traps and Ni(I )intermediates that can be trapped in the presence of halide ions to give previously characterized, stable Ni-I halogen complexes. In addition, treatment of the bromo complexes [(Me₄PNPR)(NiBr)-Br-II]BPh₄ with a powerful hydride source, LiBEt₃H, leads to the reduction of the pyridine ring and the formation of Ni-II complexes with an anionic amide donor reduced pincer ligand, although aromatic Ni-II hydride complexes could also be obtained with a weaker hydride source. We have observed that steric bulk at the phosphine donors controls the reactivity of the resulting Ni(II)H( )complexes. While t-Bu-substituted [(Me₄PNPtBu) (NiH)-H-II]Y(Y=BPh₄, B(Ar-F)(4)) does not react with O-2, the less sterically hindered Pr-i-substituted [(Me₄PNPiPr)(NiH)-H-II]Y reacts instantaneously to give an unstable superoxide adduct that can be observed by EPR. | |||||
出版者 | ||||||
出版者 | American Chemical Society | |||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 0276-7333 | |||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 1520-6041 | |||||
DOI | ||||||
関連タイプ | isVersionOf | |||||
識別子タイプ | DOI | |||||
関連識別子 | info:doi/10.1021/acs.organomet.9b00558 | |||||
権利 | ||||||
権利情報 | © 2019 American Chemical Society | |||||
権利 | ||||||
権利情報 | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Nickel(II) Complexes with Electron-Rich, Sterically Hindered PNP Pincer Ligands Enable Uncommon Modes of Ligand Dearomatization, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.organomet.9b00558. | |||||
関連サイト | ||||||
識別子タイプ | DOI | |||||
関連識別子 | https://doi.org/10.1021/acs.organomet.9b00558 | |||||
著者版フラグ | ||||||
出版タイプ | AM | |||||
出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa |