Theoretical Study of Solvent-Exchange Reactions on Hexasolvated Divalent Cations in the First Transition Series: Model Calculation of a Hydrogen Cyanide Exchange

• Wasada-Tsutsui Yuko

  Institute of Natural Sciences, Nagoya City University

• Wasada Hiroaki

  Faculty of Regional Studies, Gifu University

• Funahashi Shigenobu

  Laboratory of Analytical Chemistry, Graduate School of Science, Nagoya University

抄録

The stability of divalent cations (M(II)) of the first transition series, penta-, hexa-, and heptasolvated by hydrogen cyanide was studied in order to clarify the reaction mechanisms of nitrile-exchange reactions. The structural stabilities of the [M(NCH)₇]²⁺s depend on the d-electron configurations, though all of the [M(NCH)₅]²⁺s and [M(NCH)₆]²⁺s are located at the local minima. The [M(NCH)₇]²⁺s are structurally more stable than the heptahydrated analogues. Successive binding energies show that it is difficult for an incoming ligand to penetrate the first solvation shells of cations in the later members. Thus, the associative mechanism of solvent-exchange reactions is favorable for cations in the earlier members resulting from energetics as well as structural stability. The symmetry of the imaginary vibrational mode along the reaction path corresponds to that of the transition density induced by one-electron excitation from the antibonding orbital occupied in the d³ ion to the 4s orbital. The stable [M(NCH)₇]²⁺s arise from the large excitation energies sufficient to reduce the second term (see Eq. 4 in the text) of Bader–Pearson’s second-order perturbation expansion.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 76 (9), 1713-1722, 2003

  公益社団法人 日本化学会

キーワード

• General Chemistry

詳細情報

• CRID: 1390282679104003712
• NII論文ID: 130004151535
• NII論文ID: 10013952668
• NII書誌ID: AA00580132
• DOI: 10.1246/bcsj.76.1713
• ISSN: 13480634
• ISSN: 00092673
• NDL書誌ID: 6679832
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I6679832
• Web Site: https://academic.oup.com/bcsj/article-pdf/76/9/1713/56263973/bcsj.76.1713.pdf
• 本文言語コード: en
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