Structural difference due to intramolecular stacking interactions in dinuclear rhodium(III) complexes [{Rh(eta(5)-C5Me5)(L)}(2)](n+) containing pyrimidine-2-thionate and related ligands

摘要

Self-assembling reactions between [Rh(eta(5)-C5Me5)(H2O)(3)](2+) and pyrimidine-2-thionate (pymt) or related ligands [L; mpymt=4-methyl-pyrimidine-2-thionate(1-), dmpymt=4,6-dimethylpyrimidine-2-thionate(1-), apymt= 4-aminopyrimidine-2-thionate(1-), dapymt=4,6-diaminopyrimidine-2-thionate(1-), or mpol=2-sulfanyl-3-pyridinolate(2-)] were carried out and the products characterized by UV/vis, NMR spectroscopy, electrospray ionization mass spectrometry, and crystal structure analysis. All products are dinuclear rhodium(III) complexes of [{Rh(eta(5)-C5Me5)(L)}(2)](n+): three crystal structures with mpymt, dmpymt and mpol were determined. The mpymt and dmpymt ligands co-ordinate through a 1 kappa(2)N,S:2 kappa S mode and the two pyrimidine rings are located in cis position, whereas mpol adopts a five-membered chelating mode with 1 kappa(2)S,O:2 kappa S and the two pyrimidine rings are located in trans position. Such structural difference can reasonably be explained by the intramolecular stacking interaction between the two bridging ligands. [References: 17]