[CpRu(PMe3)2(SCHC6H4Cl-4)]PF6 | 157472-49-6

• 英文名称: [CpRu(PMe3)2(SCHC6H4Cl-4)]PF6
• CAS: 157472-49-6
• 化学式: C₁₈H₂₈ClP₂RuS*F₆P
• 分子量: 619.921
• InChiKey: VTAPQCSTFMSMDB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  、 tritylium hexafluorophosphate 以 二氯甲烷 为溶剂， 以53%的产率得到[CpRu(PMe3)2(SCHC6H4Cl-4)]PF6
  参考文献：
  名称：

  Die koordinationschemie CS-funktioneller verbindungen

  摘要：

  Hydride abstraction from [Cp(R3P)2Ru(SCH2C6H4X)] [R3P = Ph3P, Me3P, (MeO)3P; (R3P)2 = Ph2PCH2PPh2 (dppm), Ph2PC2H4PPh2(dppe), Ph2PC2H4PMe2 (dpme), Me2PC2H4PMe2(dmpe); X = H, Cl, OMe] using triphenylcarbenium hexafluorophosphate yields ionic thiobenzaldehyde complexes [Cp(R3P)2Ru(S = CHC6H4X)]PF6. With bulky ligands R3P only eta1(S) isomers are formed, whereas a dynamic eta1/eta2 equilibrium is observed for (R3P)2 = (Me3P)2, dmpe. An X-ray structure determination was carried out on [Cp(dppe)Ru(S=CHC6H4OMe)]PF6 . 0.5 Et2O (triclinic, space group P1BAR, a = 11.372(4) angstrom, b = 12.782(5) angstrom, c = 14.548(4) angstrom, alpha = 70.33(l), beta = 80.61(2)-degrees, gamma = 81.91(2)-degrees, Z = 2): Ru-PI: 2.296(l) angstrom, Ru-P2: 2.301(l) angstrom, Ru-S: 2.314(l) angstrom, S-C6: 1.632(5) angstrom. Control experiments show that the beta-hydride abstraction is initiated by single electron oxidation of the thiolate complex to give a radical cation intermediate. A fairly large kinetic isotope effect (KIE) of the H-transfer step (k(H)/k(D) = 5.6 using [Ph3C]+ and 7.4 using [CP2Fe]+ as oxidant) demonstrates that the ruthenium atom is not involved. The thiobenzaldehyde complexes readily add nucleophiles such as H-, D-, PMe3, OR-, SR-, and carbanions. With (R3P)2 = dpme, moderate diastereoselectivities are found in some of these reactions. [4 + 2]-Cycloadditions have been carried out with 2,3-dimethylbutadiene and cyclopentadiene. The latter are moderately diastereoselective for (R3P)2 = dpme and highly exo-selective for (R3P)2 = dppm. An X-ray structure determination of [Cp(dppm)-Ru(SC6H7C6H4Cl)]PF6 . MeCN (monoclinic, space group P2 1/c, a = 13.463(6) angstrom, b = 16.071(3) angstrom, c = 20.813(9) angstrom, beta = 92.30(2)-degrees, Z = 4) reveals that the E configuration of the C = S bond is retained in the Diels-Alder adduct.

  DOI：

  10.1016/0022-328x(94)80212-2