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ニトロシル錯体の合成・構造決定とab initio計算による物性解釈

Research Project

Project/Area Number 12640548
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOkayama University of Science

Principal Investigator

SHIBAHARA Takashi  Okayama University of Science, Department of Chemistry, Professor, 理学部, 教授 (30122386)

Co-Investigator(Kenkyū-buntansha) SAKANE Genta  Okayama University of Science, Department of Chemistry, Instructor, 理学部, 講師 (90278911)
Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2002: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2001: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2000: ¥2,100,000 (Direct Cost: ¥2,100,000)
KeywordsNitrosyl complexes / Chromium / Ammine / X-ray structure / Hydrogen bonding / Outer sphere anion / ab initio / 一酸化窒素 / クロム錯体 / 赤外吸収 / 固体反射スペクトル / 対イオン / ab initio計算 / 最適化構造
Research Abstract

Several kinds of nitrosylpentaamminechromium (III) complexes [Cr(NO)(NH_3)_5]^<2+> (A) with different anions were prepared and widely characterized, and it was reported that the colors in the solid states of the compounds containing A's depended very much on the kinds of counter anions. None of the crystal structures, however, were determined, and the cause of the color change was unclear for a long time.
We have succeeded in the X-ray structural determination of five kinds of the complexes, and found very little dimensional differences of the cations. However, the color, shortest O(NO)-H(NH_3 in the adjacent cation) distance (Å), peak position of reflection spectra (nm), wave number of N-O stretching vibration (cm^<-1>) of the complex compounds change considerably : A(PF_6)_2 (red, 2.399, 579, 1693, 180), ACl_2 (red-orange, 2.749, 588, 1683), ACl(ClO_4) (brown, 3.127, 598, 1710), ACl(PF_6) (brown, 3.258, 603, 1713), and A(ClO_4)_2 (green, 3.595, 623, 1728). Comparison of the five crystal structures has led to the conclusion that the existence of the strong hydrogen bonds between the O (nitrosyl) and H (ammonia in adjacent complex cations) atoms gives red crystals of A(PF_6)_2, while the absence of hydrogen bonds results in the formation of green crystals of A(ClO_4)_2.
Optimized structures of the complex A at three different spin multiplicities, doublet (A2), quartet (A4), and sextet (A6), were obtained by ab initio calculation at B3LYP/6-31G^★(6-31+G for NO) level of theory. The complex was most stable at the lowest spin multiplicity (doublet), which is in harmony with the X-ray structure of A in A(ClO_4)_2 and with the previous magnetic measurement (μ_<eff> = 1.8 BM) of A(ClO_4)_2.
Optimized structures of the complexes, [Cr(NO)(CN)_5]^<3->, [Cr(CN)(NH_3)_5]^<2+>, [Cr(N_2)(NH_3)_5]^<3+>, [Cr(CO)(NH_3)_5]^<3+>, [Cr(O_2)(NH_3)_5]^<3+> were obtained, while only the X-ray structure of [Cr(NO)(CN)_5]^<3-> has been determined among them.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report

Research Products

(10 results)

All Other

All Publications (10 results)

  • [Publications] T.Shibahara: "DET Calculation and X-Ray Structure of Nitrosyl Pentaammine Chromium Complex"Inorg. Chem. Commun.. 4. 413-415 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Akashi: "Pentaamminenitrosyl chromium (III) chloride"Acta Crystallogr.. E57. i75-i76 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Akashi: "Effect of outer sphere anions on the structure and color of nitrosylpentaamminechromium complex"Inorg. Chim. Acta. 331. 290-295 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Shibara., H.Akashi., M.Asaso., K.Wakamatsu., K.Nishimoto., and M.Mori.: "DFT Calculation and X-Ray Structure of Nitrosyl Pentaammine Chromium Complex"Inong. Chem. Commun.. 4. 413-415 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Akashi., M.Mori., and T.Shibahara.: "Pentaamminenitrosyl chromium (III) chloride"Acta Crystallogr.. E57. i75-i76 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Akashi., M.Nishiura., M.Mori., and T.Shibahara.: "Effect of outer sphere anions on the structure and color of nitrosylpentaammine chromium complex"Inorg. Chim. Acta.. 331. 290-295 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Akashi: "Effect of outer sphere anions on the structure and color of nitrosylpentaammin echromium complex"Inorg. Chim. Acta. 331. 290-295 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Shibahara: "DFT Calculation and X-Ray Structure of Nitrosyl Pentaammine Chromium Complex"Inorg. Chem. Commun.. 4. 413-415 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] H.Akashi: "Pentaamminenitrosyl chromium (III) chloride"Acta Crystallog.. E57. 175-176 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] H.Akashi: "Effect of outer sphere anions on the structure and color of nitrosylpentaamminechromium complex"lnorg. Chim. Acta. (in press).

    • Related Report
      2001 Annual Research Report

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Published: 2000-03-31   Modified: 2016-04-21  

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