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https://hdl.handle.net/2440/81480
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Type: | Journal article |
Title: | Straight forward access to tetrametallic complexes with a square array by oxidative dimerization of organometallic wires |
Author: | Burgun, A. Gendron, F. Schauer, P. Skelton, B. Low, P. Costuas, K. Halet, J. Bruce, M. Lapinte, C. |
Citation: | Organometallics, 2013; 32(18):5015-5025 |
Publisher: | Amer Chemical Soc |
Issue Date: | 2013 |
ISSN: | 0276-7333 1520-6041 |
Statement of Responsibility: | Alexandre Burgun, Frédéric Gendron, Phil A. Schauer, Brian W. Skelton, Paul J. Low, Karine Costuas, Jean-François Halet, Michael I. Bruce and Claude Lapinte |
Abstract: | The bimetallic ruthenium complex {Cp(dppe)Ru}2(μ-Cî - CCî - CCî - C) (3; Cp = cyclopentadienyl, dppe = 1,2-bis(diphenylphosphino)ethane) has been prepared and the molecular structure determined. The cyclic voltammogram of 3 is characterized by three reversible one-electron events with a large potential difference between the two first waves (ΔE = 0.44 V), indicating the large thermodynamic stability of the MV (mixed-valence) 3(PF6), which can be considered as a class III MV complex. The complex 3(PF6) was quantitatively prepared by treatment of 3 with 1 equiv of [FeCp2](PF6) at -78 C and characterized by EPR spectroscopy. Above -10 C, solutions of 3(PF6) provide the asymmetric tetranuclear complex {cyclo-C([Ru])C(CCCC[Ru])C(CC[Ru]) C(CC[Ru])}(PF6)2 (4(PF6)2; [Ru] = Cp(dppe)Ru) which was formed regiospecifically and isolated in 92% yield. Thus, despite the thermodynamic stability of the monocation radical 3(PF6) as evidenced by the electrochemical data, and the extensively delocalized electronic structure, a slow dimerization reaction takes place, affording a stable, tetranuclear complex. The new compound was characterized by a single-crystal X-ray diffraction study, cyclic voltammetry, and multinuclear NMR, IR, UV-vis, and near-IR spectroscopy, and the data were analyzed with the support of quantum chemical investigations at the DFT level of theory. The regiospecificity of the dimerization reaction is controlled by a balance of steric and electronic factors, which favors intermolecular (Cα + Cγ) radical coupling. © 2013 American Chemical Society. |
Rights: | Copyright © 2013 American Chemical Society |
DOI: | 10.1021/om4003768 |
Published version: | http://dx.doi.org/10.1021/om4003768 |
Appears in Collections: | Aurora harvest Chemistry and Physics publications |
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