| 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
Okinaka, Takaaki
Mimura, Yasuyuki
Watanabe, Mitsuko
Matsuzaki, Takayuki
Hasuoka, Atsushi
Yamamoto, Yohsuke
Matsukawa, Shiro
Akiba, Kin-ya
|
| 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 |
ChemEurJ_13-9_2517.pdf (1.2 MB)
