RUTHENIUM(II)-DIMETHYL SULFOXIDE COMPLEXES WITH NITROGEN LIGANDS - SYNTHESIS, CHARACTERIZATION AND SOLUTION CHEMISTRY - THE CRYSTAL-STRUCTURES OF CIS,FAC-RUCL2(DMSO)3(NH3) AND TRANS,CIS,CIS-RUCL2(DMSO)2(NH3)2.H2O

In this paper we report the synthesis and characterization of some new derivatives of the isomers cis-(1) and trans-RuCl2(DMSO)4 (6) (DMSO = dimethyl sulfoxide) with monodentate nitrogen donor ligands (L) such as NH3, imidazole (Im) and benzimidazole (BzIm): cis,fac,-RuCl2(DMSO)3(L) (L = NH3 (2), Im (3); cis,cis,cis-RuCl2(DMSO)2(Im)2 (4); fac-[Ru(Im)3Cl(DMSO)2]PF6 (5); trans,cis,cis-RuCl2(DMSO)2(L)2 (L = NH3 (7), Im (8), BzIm (9)); trans,-RuCl2(DMSO)3(Im) (10). All complexes have exclusively S-bonded DMSOs. Their chemical behavior in aqueous solution is also described. The crystal structures of cis,fac-RuCl2(DMSO)3(NH3) (2) and trans,cis,cis-RuCl2(DMSO)2(NH3)2.H2O (7), were determined by three dimensional X-ray analyses. Crystal data: 2, a = 9.103(2), b = 12.568(2), c = 13.375(6) angstrom, beta = 96.52(2)-degrees, monoclinic, space group P2(1)/n, Z = 4; 7, a = 8.507(4), b = 11.331(4), c = 14.071(4) angstrom, beta = 90.99(1)-degrees, monoclinic, space group P2(1)c, Z = 4. Least-squares refinement based on 4045 (2) and 3682 (7) reflections converged to R = 0.026 and 0.030 for 2 and 7, respectively. In 2, the three DMSOs have Ru-S bond distances of 2.2774(6) and 2.2458(5) angstrom (trans to Cl), and 2.2877(5) angstrom (trans to N). The Ru-Cl bond distances are 2.4178(6) and 2.4411(6) angstrom (trans to S), while the Ru-N (trans to S) bond length is 2.151(2) angstrom. In 7, the trans Ru-Cl bond distances are 2.4030(7) and 2.4125(7) angstrom, while the Ru-S (trans to N) bond distances are 2.2350(6) and 2.2469(6) angstrom, and the Ru-N (trans to S) 2.142(2) and 2.156(2) angstrom.