| People | Locations | Statistics |
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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Bruce, M. I.
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Topics
Publications (6/6 displayed)
- 2013Straightforward Access to Tetrametallic Complexes with a Square Array by Oxidative Dimerization of Organometallic Wirescitations
- 2010Syntheses and molecular structures of some tricobalt carbonyl clusters containing 2,4,6-trimethyl-1,3,5-trithianecitations
- 2007Structural and Spectroscopic Studies of Halocuprate(I) and Haloargentate(I) Complexes [M2XnX′4−n]2−citations
- 2007Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(μ-C=CC=C)]citations
- 2006Polymetallation of alkenes: Formation of some complexes containing branched chain carbon-rich ligandscitations
- 2003Crystal and Molecular Structures of Some Alkynyl-Group 9/Group 11 Complexes [M2m4(C2R)8(PPh3)2](M = Rh, Ir; m = Cu, Ag; R = Ph, Fc (Ir/Cu only))citations
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article
Straightforward Access to Tetrametallic Complexes with a Square Array by Oxidative Dimerization of Organometallic Wires
Abstract
The bimetallic ruthenium complex {Cp(dppe)Ru}2(μ-C≡CC≡CC≡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.