Coordination chemistry of diphenylphosphinoferrocenylthioethers on cyclooctadiene and norbornadiene rhodium(i) platforms |
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Authors: | Ekaterina M Kozinets Oleksandr Koniev Oleg A Filippov Jean-Claude Daran Rinaldo Poli Elena S Shubina Natalia V Belkova Eric Manoury |
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Institution: | CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France. eric.manoury@lcc-toulouse.fr. |
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Abstract: | Complexes RhCl(diene)(P,SR)] with chiral ferrocenyl phosphine-thioethers ligands (diene = norbornadiene, NBD, 1(R), or 1,5-cyclooctadiene, COD, 3(R); P,SR = CpFe(1,2-η(5)-C(5)H(3)(PPh(2))(CH(2)SR); R = tBu, Ph, Bz, Et) and the corresponding Rh(diene)(P,SR)]BF(4)] (diene = NBD, 2(R); COD, 4(R)) have been synthesized from RhCl(diene)](2) and the appropriate P,SR ligand. The molecular structure of the cationic complexes 2(tBu), 4(Ph) and 4(Bz), determined by single-crystal X-ray diffraction, shows the expected slightly distorted square planar geometry. For the neutral chloride complexes, a combination of experimental IR and computational DFT investigations points to an equally four coordinate square planar geometry with the diene ligand, the chlorine and the phosphorus atoms in the coordination sphere and with a dangling thioether function. However, a second isomeric form featuring a 5-coordinated square planar geometry with the thioether function placed in the axial position is easily accessible in some cases. |
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