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Issue 38, 2012
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Coordination chemistry of diphenylphosphinoferrocenylthioethers on cyclooctadiene and norbornadiene rhodium(i) platforms

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Abstract

Complexes [RhCl(diene)(P,SR)] with chiral ferrocenyl phosphine–thioethers ligands (diene = norbornadiene, NBD, 1RRR, or 1,5-cyclooctadiene, COD, 3RR; P,SR = CpFe(1,2-η5-C5H3(PPh2)(CH2SR); R = tBu, Ph, Bz, Et) and the corresponding [Rh(diene)(P,SR)][BF4] (diene = NBD, 2RR; COD, 4RR) have been synthesized from [RhCl(diene)]2 and the appropriate P,SR ligand. The molecular structure of the cationic complexes 2tButtButttBu, 4PhPh and 4BzBzBz, 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.

Graphical abstract: Coordination chemistry of diphenylphosphinoferrocenylthioethers on cyclooctadiene and norbornadiene rhodium(i) platforms

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Article information


Submitted
07 May 2012
Accepted
30 Jul 2012
First published
01 Aug 2012

Dalton Trans., 2012,41, 11849-11859
Article type
Paper

Coordination chemistry of diphenylphosphinoferrocenylthioethers on cyclooctadiene and norbornadiene rhodium(I) platforms

E. M. Kozinets, O. Koniev, O. A. Filippov, J. Daran, R. Poli, E. S. Shubina, N. V. Belkova and E. Manoury, Dalton Trans., 2012, 41, 11849
DOI: 10.1039/C2DT30993A

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