Synthesis and Dynamic Behaviour of Rhodium(I) Complexes containing the Di-2-pyridyl Sulphide Ligand

Article abstract of DOI:10.1039/DT9910000425

The complex X 1 (cod = cycloocta-1,5-diene; dps = di-2-pyridyl sulphide; X = BF4, PF6 or ClO4) has been prepared by reaction of dps and AgX with <(Ru(μ-Cl)(cod))2>; X 2 can be prepared by a similar route but higher yields are obtained by bubbling CO through a CH2Cl2 solution of 1.Triphenyl-phosphine or -arsine easily replaces a molecule of CO in 2 to give X 3 or X 4.These compounds have been characterized by usual spectroscopic techniques which indicate a N,N-inside conformation fo the chelate dps ligand.The reaction of <(Rh(μ-Cl)(cod))2> with dps gives rise to stoichiometry- concentration-, solvent- and temperature-dependent equilibria in which the starting materials, the binuclear complex <(Rh(cod)Cl)2(μ-dps)> 5a, +, - and Cl- are involved.Complex 5a and Cl is present only in solution.Conductivity measurements and electronic spectra indicate that the ionic species are stabilized in methanol, whereas in CH2Cl2 the starting materials and binuclear species dominate at low and higher concentration respectively.Proton and 13C NMR spectra, in CD2Cl2 indicate that exchange of the Rh(cod) unit between the starting materials, binuclear and ionic species occurs rapidly in the NMR time-scale at room temperature.When dps is added to 5a or 5b (molar ratio 1:1) the concentration of the binuclear species decreases and an equilibrium occurs between Cl and where the dps ligand is monodentate.

Full text of DOI:10.1039/DT9910000425

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