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Synthesis, structure, and properties of a lantern-type dinuclear rhodium(II) complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2], 4-Me-pf− = N,N′-di-p-tolylformamidinate anion

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Abstract

A lantern-type dinuclear complex cis-[Rh2(4-Me-pf)2(O2CCF3)2] (1) (4-Me-pf− = N,N′-di-p-tolylformamidinate anion) was reacted with an excess of pivalic acid in an aqueous NaOH solution with CHCl3/MeOH (1:3 vol./vol.) at room temperature for 24 h with stirring to give cis-[Rh2(4-Me-pf)2(O2CCMe3)2] (2). A single crystal obtained by recrystallization of 1 from an acetonitrile solution was employed for X-ray crystal structure analysis. The analysis showed that the obtained complex was a cis-[Rh2(4-Me-pf)2(O2CCMe3)2(MeCN)2] (2(MeCN)2) with a lantern-type dinuclear structure and a cis-(2:2) arrangement of the two formamidinato and two carboxylato ligands around the dirhodium(II) core, similar to the previously reported crystal structures for 1(H2O)2·0.5C6H6 and 1(MeCN)2. Complex 2 showed absorption bands at 613, 506, 435, and 344 nm in MeCN, while complex 1 showed the bands at 516, 460, and 326 nm in MeCN. All the bands observed for 1 and 2 were reasonably assigned using time-dependent density functional theory calculation. Moreover, it was confirmed that the electron-donating t-butyl groups on the carboxylato bridges of 2 give rise to negative shifts in the redox potentials (E 1/2 = 0.32 and 1.22 V (vs. SCE) in CH2Cl2) for Rh II,II2 /Rh II,III2 and Rh II,III2 /Rh III,III2 processes relative to those of 1 (E 1/2 = 0.71 and 1.47 V (vs. SCE) in CH2Cl2) that has electron-withdrawing fluorine groups on the carboxylate bridges.

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Acknowledgements

This work has been supported by a Grant-in-Aid for Scientific Research (Nos. 26410080, 15K17897, 15H00877, 16K05722) from the Ministry of Education, Culture, Sports and Technology (MEXT), Japan. The authors are grateful to Dr. Michiko Egawa (Shimane University) for her measurements of elemental analysis.

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Authors and Affiliations

  1. Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, Matsue, 690-8504, Japan

    Makoto Handa, Satoshi Nishiura, Takafumi Masuda, Natsumi Yano & Yusuke Kataoka

  2. 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

    Masahiro Mikuriya

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  1. Makoto Handa
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  2. Satoshi Nishiura
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Correspondence to Makoto Handa.

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Crystallographic data for the structure of complex 2(MeCN)2 reported in this paper have been deposited with the Cambridge Crystallographic Data Centre, CCDC no. 1537380. Copies of the information may be obtained free of charge from: The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or via http://www.ccdc.cam.ac.uk/conts/retrieving.html (PDF 4316 kb)

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Handa, M., Nishiura, S., Masuda, T. et al. Synthesis, structure, and properties of a lantern-type dinuclear rhodium(II) complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2], 4-Me-pf− = N,N′-di-p-tolylformamidinate anion. Chem. Pap. 72, 841–851 (2018). https://doi.org/10.1007/s11696-017-0244-2

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