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Syntheses, crystal and solution structures, ligand exchange, and ligand coupling reactions of mixed pentaarylantimony compounds

https://hiroshima.repo.nii.ac.jp/records/2006632
https://hiroshima.repo.nii.ac.jp/records/2006632
03d5ddd6-129c-42e1-80a1-008d50879623
名前 / ファイル ライセンス アクション
ChemEurJ_13-9_2517.pdf ChemEurJ_13-9_2517.pdf (1.2 MB)
Item type デフォルトアイテムタイプ_(フル)(1)
公開日 2023-03-18
タイトル
タイトル Syntheses, crystal and solution structures, ligand exchange, and ligand coupling reactions of mixed pentaarylantimony compounds
言語 en
作成者 Schröder, Günter

× Schröder, Günter

en Schröder, Günter

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Okinaka, Takaaki

× Okinaka, Takaaki

en Okinaka, Takaaki

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Mimura, Yasuyuki

× Mimura, Yasuyuki

en Mimura, Yasuyuki

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Watanabe, Mitsuko

× Watanabe, Mitsuko

en Watanabe, Mitsuko

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Matsuzaki, Takayuki

× Matsuzaki, Takayuki

en Matsuzaki, Takayuki

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Hasuoka, Atsushi

× Hasuoka, Atsushi

en Hasuoka, Atsushi

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Yamamoto, Yohsuke

× Yamamoto, Yohsuke

en Yamamoto, Yohsuke

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Matsukawa, Shiro

× Matsukawa, Shiro

en Matsukawa, Shiro

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Akiba, Kin-ya

× Akiba, Kin-ya

en Akiba, Kin-ya

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アクセス権
アクセス権 open access
アクセス権URI http://purl.org/coar/access_right/c_abf2
権利情報
権利情報 Copyright (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
主題
主題Scheme Other
主題 antimony
主題
主題Scheme Other
主題 hypervalent compounds
主題
主題Scheme Other
主題 ligand effects
主題
主題Scheme Other
主題 ligand-coupling
主題
主題Scheme Other
主題 structure elucidation
主題
主題Scheme NDC
主題 430
内容記述
内容記述 All the possible combinations of mixed pentaarylantimony compounds bearing p-methylphenyl and p-trifluoromethylphenyl groups were synthesized, i.e., ArnTol5-nSb (n = 0-5: Ar = p-CF3C6H4, Tol = p-CH3C6H4): Tol5Sb (1), ArTol4Sb (2), Ar2Tol3Sb (3), Ar3Tol2Sb (4), Ar4TolSb (5), and Ar5Sb (6). Compounds 2-5 are the first well-characterized examples of mixed acyclic pentaarylantimony species. The structures of 2-6 were determined by X-ray crystallography to bear trigonal bipyramidal (TBP) geometry with the more electronegative p-trifluoromethylphenyl substituents selectively occupying the apical positions. Considerations based upon the chemical shifts of the ipso carbons of the aryl and the tolyl groups suggested that the solution structures of 1-6 were also TBP although pseudorotation of them could not be frozen even at –80 °C. Ligand exchange reactions (LERs) were found to take place between 1 and 6 at ca. 60 °C in [D6]benzene and all the six species 1-6 were found in the equilibrium mixture. The relative stabilities of 1-6 were determined quantitatively by comparison of the observed molar ratios of 1-6 in equilibrium with calculated statistical molar ratios, and Ar2Tol3Sb (3) was found to be the most stable. The ligand coupling reactions (LCRs) from 2-5 in solution were found to be greatly accelerated by adding Cu(acac)2 or Li+TFPB– [TFPB: B(3,5-(CF3)2C6H3)4], with the rate becoming comparable with the LER. The use of flash vacuum thermolysis (FVT) allowed the LCR to occur with very little ligand exchange except in the case of ArTol4Sb where it was very fast. The selectivities of LCRs determined by the yield of the formed biaryls by FVT were highly consistent with those in the catalyzed reactions in solution, where bitolyl was not obtained at all. The experimental results suggested that the LCR of pentaarylantimony compounds proceeds in the manner of apical-apical coupling.
言語 en
出版者
出版者 Wiley-VCH Verlag GmbH
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
出版タイプ
出版タイプ AO
出版タイプResource http://purl.org/coar/version/c_b1a7d7d4d402bcce
関連情報
識別子タイプ DOI
関連識別子 10.1002/chem.200601439
関連情報
識別子タイプ DOI
関連識別子 http://dx.doi.org/10.1002/chem.200601439
収録物識別子
収録物識別子タイプ ISSN
収録物識別子 0947-6539
収録物識別子
収録物識別子タイプ NCID
収録物識別子 AA11076269
開始ページ
開始ページ 2517
書誌情報 Chemistry - A European Journal
Chemistry - A European Journal

巻 13, 号 9, p. 2517-2529, 発行日 2007
旧ID 20646
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