Abstract
The solvento species obtained by the treatment of cis-RuCl2(N,N-L)2 [L = di-2-pyridyl sulfide (dps), di-2-pyrimidyl sulfide (dprs)] with AgPF6, reacted with dithioethers L′ [L′ = 2,6-bis(2-pyridylthiomethyl)pyridine (pytmp), 2,6-bis(2-pyrimidylthiomethyl)pyridine (prtmp) and 2,6-bis{2-(4-methyl)pyrimidylthiomethyl} pyridine (mprtmp)] to afford the compounds [Ru(N,N-L)2(N,S-L′)][PF6]2. The 1H NMR spectra indicate that L′ is chelated through S and N atoms with the formation of a four-membered ring. As a consequence, the ruthenium and sulfur atoms are stereogenic centers with ∆ and Λ and (R) and (S) configurations, respectively. NMR spectra, at low temperatures, show that two invertomers, of similar abundance, as enantiomeric couples ∆S, ΛR and ∆R, ΛS are present. In the methylene region, four AB systems are observed that in both the species contain two non-equivalent methylene groups. Variable-temperature NMR spectra and EXSY experiments show that the sulfur inversion produces an exchange between the invertomers. The one-dimensional band-shape analysis of the exchanging methylene signals showed that the energy barriers for the process are in the 43–52 kJ mol−1 range. The possible mechanisms of the sulfur inversion are discussed.
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11243_2009_9308_MOESM2_ESM.tif
Variable-temperature 1H NMR spectra of [Ru(dps)2(mprtmp)][PF6]2 (4); computer synthesized spectra are shown on the right (TIFF 1433 kb)
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Tresoldi, G., Di Pietro, S., Drommi, D. et al. Fluxional rearrangement in congested ruthenium(II) complexes containing pyrimidine- and/or pyridine-based dithioether ligands. Transition Met Chem 35, 151–158 (2010). https://doi.org/10.1007/s11243-009-9308-7
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DOI: https://doi.org/10.1007/s11243-009-9308-7