Issue 15, 2001
From the journal:

Journal of the Chemical Society, Dalton Transactions

Synthesis, structure and hydroformylation activity of monomer rhodium and iridium pyrimidine thiolate complexes

Sergio Rojas,a   José Luis García Fierro,a   Rosa Fandos,b   Ana Rodríguezc  and  Pilar Terreros*a  

* Corresponding authors

a Instituto de Catálisis y Petroleoquímica, CSIC, Campus UAM, Cantoblanco, 28049 Madrid, Spain
E-mail: pterreros@icp.csic.es

b Universidad de Castilla-La Mancha Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias del Medio Ambiente Toledo, Spain

c Departamento de Quimica Inorganica, Organica y Bioquimica, Escuela Técnica Superior de Ingenieros Industriales, Campus de Ciudad Real, 13071 Ciudad Real, Spain

Abstract

The reaction of dinuclear [M(μ-Cl)(COD)]2 (M = Rh, Ir) with mercaptopyrimidine and its methylated derivatives affords monomeric complexes. Depending on the nature of the solvent used, the pyrimidine behaves as both a monodentate ligand, bonded to the metal directly through the sulfur atom, and as a bidentate ligand, bonded to the metal atom through both the sulfur and a nitrogen atom, acting as a chelating ligand. Reaction of these complexes with CO yields dicarbonyl complexes through displacement of the COD ligand. Displacement of one of the CO molecules occurs in the presence of PPh3. Both rhodium and iridium phosphinated complexes may accept a second PPh3 molecule within their coordination sphere, with no displacement of the remaining CO ligand. Thiolate rhodium complexes have proved to be good catalysts in the hydroformylation reaction of 1-heptene in the presence of PPh3. The donor capacity of mercaptopyrimidine ligands has been correlated with the activity of the catalysts tested. In the present work, an increase in ligand basicity gave rise to a faster reaction. However, no significant modifications in the distribution of the final products were observed.

Graphical abstract: Synthesis, structure and hydroformylation activity of monomer rhodium and iridium pyrimidine thiolate complexes

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Article information

DOI
https://doi.org/10.1039/B101915P
Article type
Paper
Submitted
28 Feb 2001
Accepted
25 May 2001
First published
17 Jul 2001

J. Chem. Soc., Dalton Trans., 2001, 2316-2324

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Synthesis, structure and hydroformylation activity of monomer rhodium and iridium pyrimidine thiolate complexes

S. Rojas, J. L. G. Fierro, R. Fandos, A. Rodríguez and P. Terreros, J. Chem. Soc., Dalton Trans., 2001, 2316 DOI: 10.1039/B101915P

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