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Magnetochemistry 2018, 4(2), 21; https://doi.org/10.3390/magnetochemistry4020021

Synthesis, Structure and Magnetic and Electrochmical Properties of Tetrakis(benzamidato)diruthenium(II,III) Tetrafluoroborate

1
Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
2
Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Kita-Ku, Okayama 700-0005, Japan
3
Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan
*
Authors to whom correspondence should be addressed.
Received: 15 April 2018 / Revised: 22 April 2018 / Accepted: 27 April 2018 / Published: 1 May 2018
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Abstract

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. View Full-Text
Keywords: lantern-type diruthenium(II,III) complex; amidato-bridge; crystal structure; magnetic properties; quartet ground state; electrochemical properties; DFT calculation lantern-type diruthenium(II,III) complex; amidato-bridge; crystal structure; magnetic properties; quartet ground state; electrochemical properties; DFT calculation
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Handa, M.; Yano, N.; Okuno, A.; Nakai, H.; Mitsumi, M.; Mikuriya, M.; Kataoka, Y. Synthesis, Structure and Magnetic and Electrochmical Properties of Tetrakis(benzamidato)diruthenium(II,III) Tetrafluoroborate. Magnetochemistry 2018, 4, 21.

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