Structural and Spectral Characteristics of the Electrogenerated Tetracyanoethylene Dianion.

• OKUMURA Noriko

• GOTO Masashi

• UNO Bunji

抄録

Structural and spectral characteristics of the electrogenerated tetracyanoethylene dianion (TCNE^2-) were experimentally and theoretically examined. Spectroelectrochemistry of TCNE gives the spectra of TCNE^2- in CH₃CN at 220 nm, and in CH₂Cl₂ at 300 nm. These spectral characteristics are well explained by CIS/6-31G(d)and semiempirical CNDO/S-CI calculations. The bands in CH₃CN and in CH₂Cl₂ are assigned to the degenerate ¹E←¹A₁ transition at the D_2d structure and the ¹B_2u←¹A_g transition at the D_2h structure, respectively. The rotation barrier of the C=C bond in TCNE^2- is estimated by Hartree-Fock (HF), second-order Moller-Plesset perturbation (MP2) and fourth-order MP (MP4) calculations with 6-31G(d), 6-31+G(d) and 6-311+G(d) basis sets as 42-51 kJ mol^-1. The D_2d structure is most stable, and the D_2h structure represents the transition state of the internal rotation. The calculations reveal that the two-electron addition to the antibonding LUMO of TCNE causes an easy rotation around the C=C bond of TCNE^2- characterized by the formal single bond. These results show that TCNE^2- preferentially adopts D_2d and D<2h> structures in solvents depending upon the solvent nature by virtue of the easy rotation around the C=C bond.

収録刊行物

• ＣＨＥＭＩＣＡＬ　＆　ＰＨＡＲＭＡＣＥＵＴＩＣＡＬ　ＢＵＬＬＥＴＩＮ

  ＣＨＥＭＩＣＡＬ　＆　ＰＨＡＲＭＡＣＥＵＴＩＣＡＬ　ＢＵＬＬＥＴＩＮ 48 (4), 537-541, 2000

  公益社団法人 日本薬学会

キーワード

• tetracyanoethylene dianion
• spectroelectrochemistry
• structural property
• MO calculation
• rotational barrier

詳細情報

• CRID: 1390001204160168576
• NII論文ID: 130003774035
• NII論文ID: 110003635500
• NII書誌ID: AA00602100
• DOI: 10.1248/cpb.48.537
• COI: 1:CAS:528:DC%2BD3cXisVSnsr0%3D
• ISSN: 13475223
• ISSN: 00092363
• ISSN: http://id.crossref.org/issn/00092363
• NDL書誌ID: 5329180
• PubMed: 10783074
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I5329180
• Web Site: http://www.jstage.jst.go.jp/article/cpb1958/48/4/48_4_537/_pdf
• 本文言語コード: en
• データソース種別:
  • JaLC
  • NDL
  • Crossref
  • PubMed
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可