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We describe a synthetic strategy for the preparation of bis-heteroleptic polypyridyl Ru(II) complexes of the type [Ru(L1) 2 (L2)] 2+  (L1 and L2 = diimine ligands) from well-defined Ru(II) precursors. For this purpose, a series of six neutral, anionic, and cationic  cis -locked Ru(II)-DMSO complexes ( 2 – 7 ) of the general formula [Y]  fac -[RuX(DMSO–S) 3 (O–O)]  n   (where O–O is a symmetrical chelating anion: oxalate (ox), malonate (mal), acetylacetonate (acac); X = DMSO–O or Cl – ;  n  = −1/0/+1 depending on the nature and charge of X and O–O; when present, Y = K +  or PF 6  – ) were efficiently prepared from the well-known  cis -[RuCl 2 (DMSO) 4 ] ( 1 ). When treated with diimine chelating ligands (L1 = bpy, phen, dpphen), the compounds  2 – 7  afforded the target [Ru(L1) 2 (O–O)] 0/+  complex together with the undesired (and unexpected) [Ru(L1) 3 ] 2+  species. Nevertheless, we found that the formation of [Ru(L1) 3 ] 2+ can be minimized by carefully adjusting the reaction conditions: in particular, high selectivity toward [Ru(L1) 2 (O–O)] 0/+  and almost complete conversion of the precursor was obtained within minutes, also on a 100–200 mg scale, when the reactions were performed in absolute ethanol at 150 °C in a microwave reactor. Depending on the nature of L1 and concentration, with the oxalate and malonate precursors, the neutral product [Ru(L1) 2 (O–O)] can precipitate spontaneously from the final mixture, in pure form and acceptable-to-good yields. When spontaneous precipitation of the disubstituted product does not occur, purification from [Ru(L1) 3 ] 2+  can be rather easily accomplished by column chromatography or solvent extraction. By comparison, under the same conditions, compound  1  is much less selective, thus demonstrating that locking the geometry of the precursor through the introduction of O–O in the coordination sphere of Ru is a valid strategic approach. By virtue of its proton-sensitive nature, facile and quantitative replacement of O–O in [Ru(L1) 2 (O–O)] 0/+  by L2, selectively affording [Ru(L1) 2 (L2)] 2+ , was accomplished in refluxing ethanol in the presence of a slight excess of trifluoroacetic acid or HPF 6 .

cis-Locked Ru(II)-DMSO Precursors for the Microwave-Assisted Synthesis of Bis-Heteroleptic Polypyridyl Compounds