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A geometrically constraining bis(benzimidazole) ligand and its nearly tetrahedral complexes with Fe(II) and Mn(II)статья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
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Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Stibrany R.T., Lobanov M.V., Schugar H.J., Potenza J.A.
- Журнал: Inorganic Chemistry
- Том: 43
- Номер: 4
- Год издания: 2004
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 1472
- Последняя страница: 1480
- DOI: 10.1021/ic030180o
- Аннотация: 2,2'-Bis[2-(1-propylbenzimidazol-2-yl)]biphenyl), 4, and its bis complexes with Fe(II) and Mn(II) have been prepared and characterized structurally and spectroscopically. Ligand 4 adopts an open, "trans" conformation in the solid state with the benzimidazole (Bzlm) groups on opposite sides of the biphenyl unit. In its complexes with metal ions, a "cis" conformation is observed, and 4 behaves as a geometrically constraining bidentate ligand with four planar groups connected by three "hinges". Reaction of 4 with Fe(II) or Mn(II) yielded isomorphous crystals (space group Pnn2) of Fe-II(4)(2)(.)(ClO4)(2) and Mn-II(4)(2)(.)(ClO4)(2), in which the M-II(4)(2) cations exhibit distorted-tetrahedral coordination geometries (N-M-N angles, 109 +/- 11degrees) enforced by rigid, chiral nine-membered M(4) rings in the twist-boat-boat conformation. Individually, the cations show R,R or S,S stereochemistry, and the crystals are racemates. Mn-II(4)(2)(.) (ClO4)(2) exhibits a quasi-reversible Mn(II) --> Mn(III) oxidation at E-1/2 = 0.64 V; the corresponding Fe(II) --> Fe(III) oxidation occurs at E-1/2 = 1.76 V. The electrochemical stability of the Fe(III) oxidation state in this system suggests the possibility of isolating an unusual pseudotetrahedral (FeN)-N-III(Bzlm)(4) species. Ultraviolet spectra of the iron and manganese complexes are dominated by absorptions of the ligand 4 blue-shifted by approximately 2000-3000 cm(-1). Ligand-field absorptions were observed for the Fe(II) complex; those for the Mn(II) complex were obscured by tailing ultraviolet absorptions. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-spin Mn(II) complex, while for the Fe(II) complex, the falloff of the magnetic moment with decreasing temperature is indicative of zero-field splitting with D similar to 4 cm(-1).
- Добавил в систему: Лобанов Максим Владимирович