Ruthenium(II)-catalyzed thioether oxidation. 1. Synthesis of mixed sulfide and sulfoxide complexes

Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

“…When 2 equiv of chelating ligand were used, the bischelated complex trans-RuBr 2 (EtSCH 2 CH 2 SEt) 2 was obtained (Scheme 32). 264 The same authors also found that treatment of 11 with the sulfide/sulfoxide bidentate ligand PhS(CH 2 ) 2 SOPh (1-phenylsulfinyl-2-phenylScheme 30 a a S ) dms; X ) Cl or Br.…”

“…An extensive investigation was performed by Riley and co-workers, [264][265][266] with the aim of determining the nature of the active species generated in the oxygen oxidation of thioethers catalyzed by the RuX 2 (dmso) 4 complexes 8 and 11. [12][13][14] The nature of the products isolated was found to depend on the steric bulk of the thioether donor ligand.…”

“…Finally, it was found that treatment of either 8 or 11 with the sulfide/sulfoxide tridentate ligand 3-(ethylthio)-1-((3-(ethylthio)propyl)sulfinyl)-propane, EtS(CH 2 ) 3 SO(CH 2 ) 3 SEt, produced only one geometric isomer, cis,mer-RuX 2 (EtS(CH 2 ) 3 SO(CH 2 ) 3 -SEt)(dmso-S), in which the tridentate chelate ligand is meridionally coordinated to Ru(II). 265 The reactivity of 8 toward macrocyclic polydentate thioether ligands (crown thioethers) has been extensively investigated by several groups. Reaction of 8 with the cyclic bidentate ligand 1,5-dithiacyclooctane (1,5-dtco) yielded trans-RuCl 2 (1,5-dtco) 2 , while the reaction with the corresponding mixed sulfide/sulfoxide ligand 1,5-dithiacyclooctane 1-oxide (1,5-dtco-O) afforded trans-RuCl 2 (1,5-dtco-O) 2 (with a cis arrangement of the two S-bound sulfoxide moieties) (Scheme 34).…”

Oxidation of secondary alcohols byN-methylmorpholine-N-oxide (NMO) catalyzed by Ru(II) halosulfoxide complexes. A kinetic study

“…The formation of intermediate complexes between catalyst and substrate as well as the formation of Ru(IV) intermediate have been demonstrated [9]. Ru(II)halosul~bxide complexes also catalyze the oxidation of alcohols by hypochlorite [10].…”

Crystal Structure of Bromo(2,2′:6′,2″-terpyridine)(2-(phenylazo)- pyridine)ruthenium(II) Tetrafluoroborate

“…The Ru-Br bond length in the title compound (2.547(5)Å) is slightly longer than those observed in [Ru(C5H5)(CO)2Br] (2.536(2)Å) 11 but shorter than those in [Ru(Br)2(Me2SO)4] (2.601(1), 2.578(1)Å). 12 The Ru-N(azo) distance (1.960(3)Å) is shorter than the Ru-N(py) distance (2.061(3)Å) and becomes shortest among the related complexes. 2,5,6 This indicates that there is strong π-backbonding in the title compound, greater The title compound, C26H20N6BrRu(BF4), crystallizes in the centrosymmetric space group P21/n and consists of discrete complex units.…”