A Pair of Seven-Coordinate Oxorhenium Complexes: [ReIVO(tpen)]〔2+〕 and [ReVO(tpen)]〔3+〕 (tpen = N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine)

• Hai-Ying Jin

• Shinji Ikari

• Kimiko Kobayashi

書誌事項

タイトル別名

• Pair of Seven Coordinate Oxorhenium Complexes ReIVO tpen 2 and ReVO tpen 3 tpen N N N N Tetrakis 2 pyridylmethyl ethylenediamine

抄録

A pair of seven-coordinate oxorhenium complexes of N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (tpen), [ReIVO(tpen)](ClO4)2 (1) and [ReVO(tpen)](ClO4)3 (2), and its R-1,2-propylenediamine analogue (R-tppn), have been prepared. X-ray structural analyses indicate that the structure of complex cation in 1 is best described as a monocapped trigonal prism with the oxo ligand as a cap. The four pyridylmethyl nitrogen atoms are essentially planar. On the other hand, the structure of complex cation in 2 is approximated as a pentagonal bipyramid, in which the four pyridyl nitrogen atoms take a tetrahedrally distorted arrangement. The structural difference is discussed in terms of different d-electron numbers. The μeff value of 1 at 300 K is 1.99 B.M. which corresponds to S = 1/2, while 2 is diamagnetic. The complexes show a reversible redox wave (Re(IV/V)) at +0.31 V vs Ag/AgCl in 0.1 M (n-C4H9)4NPF6 acetonitrile solution. In acetonitrile–aqueous buffer solution (2 < pH < 12), in addition to a pH independent Re(IV/V) wave at +0.18 V vs Ag/AgCl, a pH-dependent quasi-reversible Re(III/IV) wave with a slope of −0.056 V/pH-unit was observed, indicating that the relevant Re(III) species is [Re(OH)(tpen)]2+. The weak absorption peaks of 1 (in acetonitrile) at 836 and 511 nm and those of 2 (in water) at 800, 633, and 408 nm may be assigned to d–d transitions, while the peaks at 428, 381, and 361 nm of 1 may be of charge transfer origin.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 77 (6), 1139-1146, 2004

  Tokyo : Chemical Society of Japan

キーワード

• General Chemistry

詳細情報

• CRID: 1523669555080261376
• NII論文ID: 10013104222
• NII書誌ID: AA00580132
• ISSN: 00092673
• ISSN: 13480634
• DOI: 10.1246/bcsj.77.1139
• NDL書誌ID: 6971410
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I6971410
• Web Site: https://academic.oup.com/bcsj/article-pdf/77/6/1139/56264647/bcsj.77.1139.pdf
• 本文言語コード: en
• NDL 雑誌分類:
  • ZP1(科学技術--化学・化学工業)
• データソース種別:
  • NDL
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