Synthesis and Characterization of Monomeric Hexacoordinated Chalcogenonium Salts Bearing 2-(2-Pyridyl)phenyl Ligands

• Soichi Sato

  Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397 , Japan

• Akihisa Ooizumi

  Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397 , Japan

• Masato Sakabe

  Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397 , Japan

• Koh Funahashi

  Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397 , Japan

• Wataru Fujita

  Faculty of Science and Technology, Seikei University, 3-3-1 Kichijoji-kitamachi, Musashino, Tokyo 180-8633 , Japan

• Satoko Hayashi

  Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama 640-8510 , Japan

• Waro Nakanishi

  Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama 640-8510 , Japan

抄録

Consecutive treatment of 2-(2-lithiophenyl)pyridine with chalcogen tetrachlorides (ChCl4; Ch = Se and Te) and KPF6 afforded the hexafluorophosphate salts of tris[2-(2-pyridyl)phenyl]selenonium [(ppy)3Se]+ ([1]+) and tris[2-(2-pyridyl)phenyl]telluronium [(ppy)3Te]+ ([2]+), respectively. The chalcogenonium salts [1][PF6] and [2][PF6] exhibit extremely high thermal stability and high melting points. Their solid-state structures revealed distorted octahedral bonding geometries with a C3-symmetrical facial configuration. Quantum chemical calculations on [1]+ and [2]+ strongly suggest that their HOMO−3s involve lone pairs of electrons (LPs) on the central chalcogen atoms, and that the three Ch–N (Ch = Se and Te) bonds are formed by LP(N)→σ*(Ch–C) donor-acceptor interactions. Based on theoretical calculations and 77Se and 125Te NMR spectral data, the C–Ch–N moieties of [1]+ and [2]+ were characterized as asymmetrical three-center four-electron σ-type bonds [σ(3c–4e)]. Both organochalcogenonium salts represent novel monomeric hexacoordinated species that bear 14 formal valence electrons (14–Se–6 and 14–Te–6, respectively). A quantum theory of atoms-in-molecules dual functional analysis predicted that the C–Ch interaction of the σ(3c–4e) C–Ch–N moiety (Ch = Se and Te) is weakly covalent, while the Se–N and Te–N interactions were predicted to have the typical characteristics of hydrogen bonds and molecular complexes, respectively. The differences between [2][PF6] and the recently reported [2][Br] were also carefully examined.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 94 (4), 1192-1200, 2021-01-29

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360850954364675456
• NII論文ID: 130008037378
• DOI: 10.1246/bcsj.20200367
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/94/4/1192/56308829/bcsj.20200367.pdf
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