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Electronic Structure of Four-Coordinate Iron(I) Complex Supported by a Bis(phosphaethenyl)pyridine Ligand

机译:双(磷乙烯基)吡啶配体负载的四配位铁(I)配合物的电子结构

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摘要

A 15-electron iron complex with a formal Fe(I) center, [FeBr(BPEP)] (BPEP = 2,6-bis(1-phenyl-2-phosphaethenyl)pyridine), was prepared by one-electron reduction of the dibromide precursor [FeBr2(BPEP)]. The single-crystal diffraction analysis revealed a distorted trigonal monopyramidal arrangement around the iron center, and SQUID magnetometry established the S = 3/2 ground state. The Mössbauer isomer shift value (δ = 0.59 mm/s) was consistent with a high-spin Fe(I) center of [FeBr(BPEP)]. DFT calculations for a model complex revealed two highly delocalized molecular orbitals formed by bonding and antibonding interactions between the dz2 (Fe) and π* (BPEP) orbitals. Orbital occupancy analysis demonstrated the electronic structure with a high-spin Fe(I) center. The effective dπ−pπ interaction between iron and BPEP was concluded to be responsible for the highly distorted structure of [FeBr(BPEP)], with its rather uncommon trigonal monopyramidal configuration.
机译:通过电子单价还原一个具有正式Fe(I)中心[FeBr(BPEP)](BPEP = 2,6-双(1-苯基-2-磷乙烯基)吡啶的15电子的铁配合物。二溴化物前体[FeBr 2 (BPEP)]。单晶衍射分析显示,铁中心周围的三角形单锥体排列变形,SQUID磁力计确定了S = 3/2基态。 Mösbauer异构体位移值(δ= 0.59 mm / s)与[FeBr(BPEP)]的高旋转Fe(I)中心一致。对模型复合体的DFT计算揭示了两个高度离域的分子轨道,这些分子轨道是由d z 2 (Fe)和π*(BPEP)轨道之间的键和反键相互作用形成的。轨道占有率分析证明了具有高旋转Fe(I)中心的电子结构。得出结论,铁与BPEP之间的有效dπ-pπ相互作用是[FeBr(BPEP)]高度扭曲的结构的原因,它具有相当罕见的三角单锥体构型。

著录项

  • 来源
    《Journal of the American Chemical Society》 |2010年第29期|p.9934-9936|共3页
  • 作者

    Yumiko Nakajima;

  • 作者单位

    Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan, Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan, and Fukui Institute for Fundamental Chemistry, Kyoto;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
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  • 入库时间 2022-08-18 00:50:19

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