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Synthesis, Structure and Magnetic and Electrochmical Properties of Tetrakis(benzamidato)diruthenium(II,III) Tetrafluoroborate
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- Makoto Handa
- Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
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- Natsumi Yano
- Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
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- Airi Okuno
- Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
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- Hiroki Nakai
- Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
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- Minoru Mitsumi
- Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Kita-Ku, Okayama 700-0005, Japan
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- Masahiro Mikuriya
- Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan
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- Yusuke Kataoka
- Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
Description
<jats:p>A lantern-type diruthenium(II,III) complex [Ru2(HNOCPh)4(BF4)(H2O)] was prepared from [Ru2(HNOCPh)4Cl]n by removal of the axial chlorido-bridge using AgBF4 in THF. The room temperature magnetic moment (per Ru25+ unit) of [Ru2(HNOCPh)4(BF4)(H2O)] is 3.84 μB, which is similar to that (4.15 μB) of [Ru2(HNOCPh)4Cl]n, for which magnetic measurement was newly performed in this study. These results indicate that both of the complexes have a spin state of S = 3/2, although temperature-variable (VT) magnetic moments (2–300 K) showed that considerable antiferromagnetic interaction (zJ = −2.8 cm−1) exists through the axial chlorido-bridge for [Ru2(HNOCPh)4Cl]n, but such a large interaction (zJ = −0.08 cm−1) does not exist for [Ru2(HNOCPh)4(BF4)(H2O)], where the large zero-field splitting D = 61 cm−1 is operative for both complexes, like other lantern-type diruthenium(II,III) complexes. The X-ray single-crystal structure analysis of [Ru2(HNOCPh)4(BF4)(H2O)]·2(acetone) showed that the axial positions of the complex were occupied by a fluorine atom of the BF4− ion and an oxygen atom of the water molecule, with distances of Ru-Fax = 2.3265(19) Å and Ru-Oax = 2.280(2) Å, respectively. The Ru-Ru bond distance was 2.2793(4) Å, which is shorter than those (2.295(2) and 2.290(2) Å) reported for [Ru2(HNOCPh)4Cl]n. The quartet ground states (S = 3/2) were reasonably interpreted for [Ru2(HNOCPh)4(BF4)(H2O)] and [Ru2(HNOCPh)4Cl]n, as well as the theoretically modeled complex cation [Ru2(HNOCPh)4]+, by DFT calculation results. A Ru26+/Ru25+ redox couple was observed at 1.12 V (vs. SCE) for [Ru2(HNOCPh)4(BF4)(H2O)] in dichloromethane containing Bu4NPF6 as electrolyte.</jats:p>
Journal
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- Magnetochemistry
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Magnetochemistry 4 (2), 21-, 2018-05-01
MDPI AG
Related Data
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Keywords
- crystal structure
- DFT calculation
- electrochemical properties
- amidato-bridge
- Chemistry
- lantern-type diruthenium(II,III) complex
- lantern-type diruthenium(II,III) complex; amidato-bridge; crystal structure; magnetic properties; quartet ground state; electrochemical properties; DFT calculation
- quartet ground state
- magnetic properties
- QD1-999
Details 詳細情報について
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- CRID
- 1360848664432815360
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- ISSN
- 23127481
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- Article Type
- journal article
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- Data Source
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- Crossref
- KAKEN
- OpenAIRE
