Schenk Wolfdieter A., Frisch Jürgen, Dürr Michael, Burzlaff Nicolai, Stalke Dietmar, Fleischer Roland, Adam Waldemar, Prechtl Frank, Smerz Alexander K.
Institut für Anorganische Chemie and Institut für Organische Chemie, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany.
Inorg Chem. 1997 May 21;36(11):2372-2378. doi: 10.1021/ic961280f.
Ionic ruthenium thioether complexes [Cp(LL')Ru(SRR')]PF(6) (LL' = Ph(2)PCH(2)PPh(2) (1), Ph(2)PC(2)H(4)PPh(2) (2), (Ph(3)P, CO) (3), Me(2)PC(2)H(4)PPh(2) (4), (S,S)-Ph(2)PCHMeCHMePPh(2) (5), SRR' = MeSPh (a), MeS-i-Pr (b), MeSBz (c), i-PrSBz (d), EtSBz (e), MeSCy (f), SC(4)H(8) (g)) were synthesized from the corresponding chloro complexes [Cp(LL')RuCl] and thioethers. 5a crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 11.269(3) Å, b = 15.104(2) Å, c = 23.177(4) Å, and Z = 4. 5b crystallized in the monoclinic system, space group P2(1) (No. 4), with a = 10.539(5) Å, b = 16.216(9) Å, c = 11.011(8) Å, beta = 106.04(2) degrees, and Z = 2. A similar ligand exchange reaction yielded the analogous sulfoxide complexes [Cp(LL')Ru(S(O)RR')]PF(6) (6-10). 10a crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 14.1664(13) Å, b = 15.792(2) Å, c = 17.641(2) Å, and Z = 4. 10b.0.93CH(2)Cl(2) crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 12.069(2) Å, b = 17.379(2) Å, c = 19.760(5) Å, and Z = 4. The thioether complexes can also be directly converted to sulfoxide complexes with the strong oxygen transfer reagent dimethyldioxirane (DMD). No crossover products are formed when mixtures of two thioether complexes (e.g., 1a/2c or 1c/2a) are treated with DMD, demonstrating that no Ru-S bond cleavage is involved. Moderate diastereoselectivities are observed for the oxygen transfer to chiral, racemic thioether complexes 3 (8-28%) and 4 (34-60%). Oxidation of the (S,S)-CHIRAPHOS complexes 5, however, is highly stereoselective (de = 46-98%). Treatment of the sulfoxide complexes 10 with sodium iodide removes the chiral, nonracemic sulfoxides from the metal with retention of the configuration at sulfur.
离子型钌硫醚配合物[Cp(LL')Ru(SRR')]PF₆（LL' = Ph₂PCH₂PPh₂ (1)，Ph₂PC₂H₄PPh₂ (2)，(Ph₃P, CO) (3)，Me₂PC₂H₄PPh₂ (4)，(S,S)-Ph₂PCHMeCHMePPh₂ (5)，SRR' = MeSPh (a)，MeS-i-Pr (b)，MeSBz (c)，i-PrSBz (d)，EtSBz (e)，MeSCy (f)，SC₄H₈ (g)）由相应的氯配合物[Cp(LL')RuCl]和硫醚合成。5a在正交晶系中结晶，空间群为P2₁2₁2₁（编号19），a = 11.269(3) Å，b = 15.104(2) Å，c = 23.177(4) Å，Z = 4。5b在单斜晶系中结晶，空间群为P2₁（编号4），a = 10.539(5) Å，b = 16.216(9) Å，c = 11.011(8) Å，β = 106.04(2)°，Z = 2。类似的配体交换反应得到了类似的亚砜配合物[Cp(LL')Ru(S(O)RR')]PF₆（6 - 10）。10a在正交晶系中结晶，空间群为P2₁2₁2₁（编号19），a = 14.1664(13) Å，b = 15.792(2) Å，c = 17.641(2) Å，Z = 4。10b·0.93CH₂Cl₂在正交晶系中结晶，空间群为P2₁2₁2₁（编号19），a = 12.069(2) Å，b = 17.379(2) Å，c = 19.760(5) Å，Z = 4。硫醚配合物也可以用强氧转移试剂二甲基二氧杂环丙烷（DMD）直接转化为亚砜配合物。当两种硫醚配合物（如1a/2c或1c/2a）的混合物用DMD处理时，不会形成交叉产物，这表明不涉及Ru - S键的断裂。在手性、外消旋硫醚配合物3（8 - 28%）和4（34 - 60%）的氧转移过程中观察到适度的非对映选择性。然而，(S,S)-CHIRAPHOS配合物5的氧化具有高度的立体选择性（de = 46 - 98%）。用碘化钠处理亚砜配合物10会从金属上除去手性、非外消旋亚砜，同时保持硫原子处的构型。
