An unprecedented up-field shift in the 13C NMR spectrum of the carboxyl carbons of the lantern-type dinuclear complex TBA[Ru2(O2CCH3)4Cl2] (TBA+ = tetra(n-butyl)ammonium cation)

Yuya Hiraoka; Takahisa Ikeue; Hiroshi Sakiyama; Frédéric Guégan; Dominique Luneau; Béatrice Gillon; Ichiro Hiromitsu; Daisuke Yoshioka; Masahiro Mikuriya; Yusuke Kataoka; Makoto Handa

doi:10.1039/C5DT01680K

An unprecedented up-field shift in the ¹³C NMR spectrum of the carboxyl carbons of the lantern-type dinuclear complex TBA[Ru₂(O₂CCH₃)₄Cl₂] (TBA⁺ = tetra(n-butyl)ammonium cation)†

Yuya Hiraoka,^a Takahisa Ikeue,*^a Hiroshi Sakiyama,^b Frédéric Guégan,^c Dominique Luneau,^c Béatrice Gillon,^d Ichiro Hiromitsu,^e Daisuke Yoshioka,^f Masahiro Mikuriya,*^f Yusuke Kataoka^a and Makoto Handa*^a

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* Corresponding authors

^a Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
E-mail: handam@riko.shimane-u.ac.jp

^b Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, 1-4-12 Kojirakawa, Yamagata 990-8560, Japan

^c Laboratoire des Multimatériaux et Interfaces (UMR 5615), Université Claude Bernard Lyon 1, Campus de La Doua, 69622 Villeurbanne Cedex, France

^d Laboratoire Léon Brillouin CEA/CNRS, UMR0012, Centre d'Etudes de Saclay, Gif sur Yvette, France

^e Department of Physics and Materials Science, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan

^f Department of Applied Chemistry for Environment and Research Center for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan

Abstract

A large up-field shift (−763 ppm) has been observed for the carboxyl carbons of the dichlorido complex TBA[Ru₂(O₂CCH₃)₄Cl₂] (TBA⁺ = tetra(n-butyl)ammonium cation) in the ¹³C NMR spectrum (CD₂Cl₂ at 25 °C). The DFT calculations showed spin delocalization from the paramagnetic Ru₂⁵⁺ core to the ligands, in agreement with the large up-field shift.

Dalton Transactions

An unprecedented up-field shift in the ¹³C NMR spectrum of the carboxyl carbons of the lantern-type dinuclear complex TBA[Ru₂(O₂CCH₃)₄Cl₂] (TBA⁺ = tetra(n-butyl)ammonium cation)†

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An unprecedented up-field shift in the ¹³C NMR spectrum of the carboxyl carbons of the lantern-type dinuclear complex TBA[Ru₂(O₂CCH₃)₄Cl₂] (TBA⁺ = tetra(n-butyl)ammonium cation)

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