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Updated: Oct 18, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Tetranuclear rollover cyclometalated organoplatinum-rhenium compounds; C-I oxidative addition and C-C reductive
S Masoud Nabavizadeh1, Hajar Molaee1, Elahe Haddadi1
1Professor Rashidi Laboratory of Organometallic Chemistry, Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71467-13565, Iran. nabavizadeh@shirazu.ac.ir.
Abstract:
The novel tetranuclear Pt(IV)-Re(VII) complex [Pt2Me4(OReO3)2(PMePh2)2(µ-bpy-2H)], 4, is synthesized through the reaction of silver perrhenate with a new rollover cycloplatinated(IV) complex [Pt2Me4I2(PMePh2)2(µ-bpy-2H)], 3. In complex 4, while 2,2'-bipyridine (bpy) acts as a linker between two Pt metal centers, oxygen acts as a mono-bridging atom between Pt and Re centers through an unsupported Pt(IV)-O-Re(VII) bridge. The precursor rollover cycloplatinated(IV) complex 3 is prepared by the MeI oxidative addition reaction of the rollover cycloplatinated(II) complex [Pt2Me2(PMePh2)2(µ-bpy-2H)], 2. Complex 2 shows a metal-to-ligand charge-transfer band in the visible region, which was used to investigate the kinetics and mechanism of its double MeI oxidative addition reaction. Based on the experimental findings, the classical SN2 mechanism was suggested for both steps and supported by computational studies. All complexes are fully characterized using multinuclear NMR spectroscopy and elemental analysis. Attempts to grow crystals of the rollover cycloplatinated(IV) dimer 3 yielded a new dimer rollover cyclometalated complex [Pt2I2(PMePh2)2(µ-bpy-2H)], 5, presumably from the C-C reductive elimination of ethane. The identity of complex 5 was confirmed by single crystal X-ray diffraction analysis.
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