Cationic ruthenium sulfine complexes [CpRu(PR´3)2(O=S=CHR)]PF6 have been obtained by a variety of methods. Oxidation of the thioaldehyde complexes [CpRu(PR´3)2(S=CHR)]PF6 with either 2-tosyl-3-phenyl-oxaziridine (PR´3 = PMe3 ) or magnesium-monoperoxyphthalate (PR´3 = 1/2 dppm) gave complexes of arylsulfines (R = Ph, 3-C6H4F, 4-C6H4Cl, 4- C6H4OMe) selectively in their thermodynamically less stable E form. Siloxane elimination from the sulfinato complexes [CpRu(PMe3)2(SO2CHRSiMe3)] yielded complexes of aliphatic sulfines, [CpRu(PMe3)2(O=S=CHR)]PF6 (R =H,Me). Treatment of [CpRu(dppm)(SO2CH2R)] with acetyl chloride led to an oxygen redistribution giving complexes of thioaldehydes [CpRu(dppm)(η2-S=CH2)]PF6 and [CpRu(dppm)(η1-S=CHR)]PF6 (R = Ph, 4-C6H4Cl). The structure of the latter was determined by X-ray crystallography. The loss of oxygen can be suppressed by performing the acylation-elimination sequence in the presence of poly-(4-vinylpyridine). This provided a selective access to complexes of Z-sulfines, [CpRu(PMe3)2(O=S=CHR)]PF6 (R = Ph, 4-C6H4Cl) and [CpRu(dppm)(O=S=CHR)]PF6 (R = Ph, 4-C6H4Cl, COOEt, Cl). Complexes of the parent sulfine O=S=CH2 were also obtained by SO transfer to the methylene complex [CpRu(PMe3)2(CH2)]PF6 and methylene transfer to the sulfur monoxide complex [Cp*Ru(PMe3)2 (SO)]PF6. Most of the new sulfine complexes exhibit dynamic behaviour in solution, i. e. ligand rotation, ligand inversion, and η2 /η1 hapticity change. O-Alkylation provided the dicationic complex [CpRu(PMe3)2 (EtO-S=CHMe)](PF6)2, and S-oxidation gave the sulfene complexes [(C5R5)Ru(PMe3)2 (O2S=CH2)]PF6 (R = H, Me).
Ruthenium-sulfur dioxide complexes [cpRu(PR3)2(SO2)]Cl ((PR3)2 = (PPh3)2, Ph2PCH2PPh2(dppm), Ph2PC2H4PPh2(dppe)) add alkoxide to give sulfito complexes [cpRu(PR3)2(SO2OR′)] (R′ = Me, Et, /Pr). Reactions of [cpRu(dppm)(SO2)]Cl with LiR′ (R′ = Me, Bu, Ph), MgBrR′ (R′ = Et, CH=CH2) or ZnEt2 give sulfinato complexes [cpRu(dppm)(SO2R′)]. The structure of [cpRu(dppm)(SO2Et)] was determined by X-ray crystallography: Crystals are triclinic, space group P1̄, a = 11,008(1), b = 15,998(6), c = 17,813(2) Å, α = 92,30(2), β = 93,916(8), γ = 107,54(2)°, Z = 4. Salient features are a short Ru-S bond and relatively long S-O bonds which attest to the high π-donor ability of the pseudo-tetrahedral metal fragment.
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