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Azidotetrakis(diarylformamidinate)diruthenium(II,III) Compounds: Synthesis, Molecular Structures and Voltammetric Properties; Linear Free Energy Relationships in Dinuclear Compounds VII*,†

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A series of Ru2(DArF)4(N3) compounds have been prepared from the metathesis reaction between Ru2(DArF)4Cl and NaN3, where DArF is diarylformamidinate, and aryl is X–Ph with X as 4-MeO (1), 4-Me (2), H (3), 3-MeO (4), 4-Cl (5), 3-Cl (6), 3-CF3 (7), 4-CF3 (8), 3,4-Cl2 (9) and 3,5-Cl2 (10). Single crystal X-ray diffraction studies of 3 and 10 revealed the expected paddlewheel motif for the first coordination sphere of Ru2 and axial ligation of azide. Voltammetric studies revealed a (quasi)reversible oxidation (A) and a irreversible reduction (B) for all compounds, and a second (quasi)reduction (C) for compounds 6–10. The half-wave potentials of couple A span a remarkable range of 640 mV, and they correlate linearly with the Hammett constant (σ) of the aryl substituent.

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Acknowledgment

This work is supported in part by the National Science Foundation (CHE0242623) and the University of Miami (CCD-diffractometer fund).

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  1. Department of Chemistry, University of Miami, Coral Gables, Florida, 33146

    Wei-Zhong Chen, Veronica De Silva, Chun Lin, Jessica Abellard, David M. Marcus & Tong Ren

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  1. Wei-Zhong Chen
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  2. Veronica De Silva
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  3. Chun Lin
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  4. Jessica Abellard
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  6. Tong Ren
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Correspondence to Tong Ren.

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1Dedicated to Professor F. Al Cotton, mentor, friend, and pioneer, on the occasion of his 75th birthday. 2For part VI, see C. Lin, T. Ren, E.J. Valente, and J.D. Zubkowski (1999). J. Organomet. Chem. 579, 114.

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Chen, WZ., De Silva, V., Lin, C. et al. Azidotetrakis(diarylformamidinate)diruthenium(II,III) Compounds: Synthesis, Molecular Structures and Voltammetric Properties; Linear Free Energy Relationships in Dinuclear Compounds VII*,†. J Clust Sci 16, 151–165 (2005). https://doi.org/10.1007/s10876-005-4403-1

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