Abstract Allyl thioether complexes [CpRu(P-P)(SRR′)]PF6 (P-P = Ph2PCH2PPh2 (dppm), Ph2PC2H4PP2 (dppe), R = Me, Et, Ph, R′ = 3-propenyl, 3-cyclohexenyl, 2-methyl-2-buten-4-yl) and [CpRu(chir)(SRR′)]PF6 (chir = (S,S)-Ph2PCHMeCHMePPh2, R = Me, CH2Ph, R′ = 2-methyl-2-buten-4-yl) are obtained from the corresponding thiolate complexes by reaction with the appropriate allyl bromide. Careful oxidation with dimethyldioxirane (DMD) gave the allyl sulfoxide complexes [CpRu(P-P)(MeS(O)CH2CH=CH2)]PF6 (P-P = dppm, dppe). Double oxidation to the corresponding sulfinylmethyl epoxide complexes can be readily achieved with an excess of DMD. Oxidation of the chir complexes proceeds with only moderate diastereoselectivity. The structure of the (R, R/S, S) diastereomer of [CpRu(dppm)(MeS(O)CH2CHCH2O)]PF6 was determined: monoclinic space group P21/c (No. 14), a = 11.21(2), b = 16.762(9), c = 18.45(4) Å, β = 94.4(1)°, Z = 4. For a representative example, the decomplexation of the sulfoxide-epoxide ligand by sodium iodide in acetone was demonstrated.
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