Abstract

In this paper we report the synthesis and characterization of the following ruthenium(II) and ruthenium(III) complexes with tetramethylene sulfoxide (TMSO): cis-RuCl 2(TMSO) 4 ( 1), trans- RuCl 2(TMSO) 4 ( 2), the corresponding dibromo derivatives cis- and trans-RuBr 2(TMSO) 4 ( 3 and 4, respectively), (TMSO)H[ trans-Ru(TMSO) 2Cl 4] ( 5) and mer-RuCl 3(TMSO) 3 ( 6). Most of the reported complexes are described here for the first time, together with a new, easy synthetic path for the previously known complexes 1 and 3. The chemical behavior of 1 and 2 in solution of aprotic, non- coordinating solvents is described. Among the Ru(II) derivatives, the cis isomers are thermodynamically more stable and a photochemically driven cis to trans isomerization reaction is observed in tetramethylene sulfoxide solution. We also report the crystal structures of cis-RuCl 2(TMSO) 4 ( 1) and (TMSO)H[ trans- Ru(TMSO) 2Cl 4] ( 5), as determined by three dimensional X-ray analyses. Crystal data: 1, a=9.104(2), b=11.317(2), c=21.867(6) Å, β=90.62(2)°, monoclinic, space group P2 1/ c, Z=4; 5, a=14.642(4), b=14.999(4), c=9.667(4) Å, β=103.57(1)°, monoclinic, space group P 1/ c, Z=4. Least-squares refinement based on 3813 ( 1) and 4706 ( 5) reflections converged to R=0.032 and 0.033 for 1 and 5, respectively. In 1, all the TMSO ligands are S-bonded to Ru, with average RuS bond distances of 2.355(6) ( trans to S) and 2.273(1) ( trans to Cl) Å. The TMSO ligands in 5 are both S-bonded to Ru (av. 2.33(1) Å). The protonated TMSO molecule is hydrogen bonded to one of the two crystallographically independent anions.

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