Theoretical Study on the Electronic Configurations and Nature of Chemical Bonds of Dirhodium Tetraacetato Complexes [Rh2(CH3COO)4(L)2] (L = H2O, Free): Broken Symmetry Approach

• Yusuke Kataoka

  Department of Chemistry, Graduate School of Science, Osaka University

• Yasutaka Kitagawa

  Department of Chemistry, Graduate School of Science, Osaka University

• Toru Saito

  Department of Chemistry, Graduate School of Science, Osaka University

• Yasuyuki Nakanishi

  Department of Chemistry, Graduate School of Science, Osaka University

• Toru Matsui

  Department of Chemistry, Graduate School of Science, Osaka University

• Konomi Sato

  Department of Chemistry, Faculty of Science, Kanagawa University

• Yuhei Miyazaki

  Department of Chemistry, Faculty of Science, Kanagawa University

• Takashi Kawakami

  Department of Chemistry, Graduate School of Science, Osaka University

• Mitsutaka Okumura

  Department of Chemistry, Graduate School of Science, Osaka University

• Wasuke Mori

  Department of Chemistry, Faculty of Science, Kanagawa University

• Kizashi Yamaguchi

  Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University

Abstract

The electronic configurations and the nature of chemical bonds of the classical lantern-type dinuclear rhodium(II) tetraacetato complexes [Rh2(CH3COO)4(L)2] (L = H2O, free) have been carefully investigated with broken symmetry (BS) Hartree–Fock (HF), BS density functional theory (DFT), and BS hybrid DFT (HDFT) methods. Several electronic configurations have been proposed for the ground states of the [Rh2(RCOO)4(H2O)2] complexes. In this study, we concluded that those different electronic configurations originate from the position of the axial H2Os, and not along the Rh–Rh length. The BS(U)B3LYP calculation indicates that the stability of the σ and δ orbitals changed when the Rh–OH2 length was 2.35 Å. The natural orbital (NO) analyses and chemical indices clearly indicate that there is a σ-type single bond between the Rh ions, and that the axial H2Os does not affect the overlap.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 83 (12), 1481-1488, 2010-11-27

  Oxford University Press (OUP)

Keywords

• General Chemistry

Details

• CRID: 1360283694073492864
• NII Article ID: 130004059006
• DOI: 10.1246/bcsj.20100128
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/83/12/1481/56272233/bcsj.20100128.pdf
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