Syntheses and structures of ruthenium(II) complexes bearing hybrid phosphine-thioether ligands, Me2PCH2CH2SR

Hybrid phosphine-thioether ligands Me2PCH2CH2SR (L) reacted with [RuCl2(cym )](2) (cym=p-cymene) to produce 11 new ruthenium(II) complexes. [RuCl2(cym) (L)] (1-3 for R=CH3(Me), C2H5(Et) and C6H5(Ph), respectively) in toluene, [ RuCl(cvm)(L)](+) (4-6 for R = Me, Et and Ph, respectively) in ethyl alcohol and [RuCl2(L)(2)] (7 and 8 for R = Me and Et, respectively and 9-11 for R = Ph) in refluxing n-butanol. Complexes 1-3 in which L acts as a monodentat e ligand through phosphorus led to complexes 4-6 where L binds to Ru throug h phosphorus and sulfur in ethyl alcohol at room temperature. Complexes 9-1 1 were separated into three of five possible geometrical isomers by fractio nal crystallization, trans(Cl,Cl')trans(P,P') (9), cis(Cl,Cl')cis(P,P') (10 ) and trans(Cl,Cl')cis(P,P') (11), whereas complexes 7 and 8 afforded only the trans(Cl,Cl')trans (P,P') isomer. The crystal structures of complexes 5 , 8, 9 and 11 were determined by an X-ray diffraction method, suggesting st ronger trans influence of the dimethytphosphino group than those of the thi oether and p-cymene moieties. P-31-{H}- and H-1- or C-13-{H}-NMR spectral d ata are used to characterize the structures of the complexes. The hydride c omplex [RuH(cym)Me2PCH2CH2SEt)](+) was also prepared by the treatment of Na BH4 with complex 5. (C) 1999 Elsevier Science S.A. All rights reserved.