[RuCl2(PPh3)([9]aneS3)] | 141738-34-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [RuCl2(PPh3)([9]aneS3)]
• CAS: 141738-34-3
• 化学式: C₂₄H₂₇Cl₂PRuS₃
• 分子量: 614.626
• InChiKey: MYRZBOZCECYEKN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.02
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  [RuCl2(PPh3)([9]aneS3)] 在 aq. KOH 作用下， 以 甲醇 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Structure and reactions of the thioether half-sandwich ruthenium(II) complexes [Ru(MeCN)3([9]aneS3)][CF3SO3]2 and [Ru(MeCN)2(PPh3)([9]aneS3)][CF3SO3]2([9]aneS3= 1,4,7-trithiacyclononane)

  摘要：

  The complex [Ru(MeCN)3([9]aneS3)][CF3SO3]2 ([9]aneS3 = 1,4,7-trithiacyclononane) was prepared by reaction of [RuCl2(dmso)([9]aneS3)] 1 (dmso = dimethyl sulfoxide) with Ag(CF3SO3) in acetonitrile. It has been employed as a starting material for the synthesis of the mixed-ligand sandwich complexes [Ru{HB(pz)3}([9]aneS3)][CF3SO3] 3 (pz = pyrazol-1-yl) and [Ru{HC(pz)3}([9]aneS3)][CF3SO3]2 4 and the dinuclear half-sandwich complex [{Ru(mu-S2CNMe2)([9]aneS3)}2][CF3SO3]2 5. The complex [Ru(MeCN)2(PPh3)([9]aneS3)][CF3SO3]2 6 may likewise be used for the preparation of thioether half-sandwich ruthenium(II) complexes such as [Ru(S2CNMe2)(PPh3)([9]aneS3)][CF3SO3] 7 and [Ru(C7H4NS2)(PPh3)([9]aneS3)][CFSO3] 8 (C7H4NS2 = 2-sulfanylbenzothiazolate). The structures of 1, 2 and 5-7 have been determined by X-ray crystallography.

  DOI：

  10.1039/dt9940001885
• 作为产物：
  描述：

  tris(triphenylphosphine)ruthenium(II) chloride 、 1,4,7-三硫环壬烷 以 not given 为溶剂， 生成 [RuCl2(PPh3)([9]aneS3)]
  参考文献：
  名称：

  Heteronuclear cluster formation: the synthesis and structure of the chloro-bridged tetranuclear complex [TlCl₂Ru(PPh₃)([9]aneS₃)]₂(PF₆)₂incorporating a [RuCl₂Tl₂Cl₂Ru] ladder ([9]aneS₃= 1,4,7-trithiacyclononane)

  摘要：

  在 273 K 的温度下，将[RuCl2(PPh3)3]与[9]eneS3 反应生成的高产率[RuCl2(PPh3)([9]aneS3)]与 TIPF6 在 CH2Cl2 中进行处理，可得到包含[RuCl2Tl2Cl2Ru]梯级的黄色杂簇物种[TlCl2Ru(PPh3)([9]aneS3)]2(PF6)2；将[TlCl2Ru(PPh3)([9]aneS3)]2(PF6)2溶解在丙酮中会导致 TlCl 沉淀，并形成橙色的氯桥二聚体[RuCl(PPh3)([9]aneS3)]2(PF6)2。

  DOI：

  10.1039/c39920000848

文献信息

• Osmium thioether chemistry: synthesis and single-crystal X-ray structures of [Os([9]aneS₃)₂][PF₆]₂·2MeNO₂, [Os(4-MeC₆H₄Prⁱ)([9]aneS₃)][BPh₄]₂·MeNO₂and [OsH(CO)(PPh₃)([9]aneS₃)]PF₆·0.5CH₂Cl₂([9]aneS₃= 1,4,7-trithiacyclononane)
  作者：Michael N. Bell、Alexander J. Blake、Robert M. Christie、Robert O. Gould、Alan J. Holder、Timothy I. Hyde、Martin Schröder、Lesley J. Yellowlees

  DOI：10.1039/dt9920002977

  日期：——

  Treatment of [OsCl2(4-MeC6H4Pri)}2] with 4 molar equivalents of [9]aneS3 in EtOH for 48 h followed by addition of NH4PF6 affords the bis(sandwich) complex [Os([9]aneS3)2][PF6]2 in 55% yield. An alternative and more direct route is by reaction of [NH4]2[OsCl6] with 2 molar equivalents of [9]aneS3 in refluxing water-dimethylformamide-MeOH (3:1:1 v/v/v) for 48 h followed by addition of NH4PF6. The complex [Os([9]aneS3)2][PF6]2.2MeNO2 crystallises in the monoclinic space group P2(1)/a (alt. P2(1)/c, no. 14) with a = 9.6621(5), b = 1 5.1 573(8), c = 10.6367(7) angstrom, beta = 100.524(5)-degrees and Z = 2. A single-crystal X-ray structure determination shows a centrosymmetric cation with homoleptic thioether co-ordination at Os(II), Os-S(1) 2.3313(18), Os-S(4) 2.3380(19) and Os-S(7) 2.3408(20) angstrom, consistent with a d6 metal centre. The ion [Os([9]aneS3)2]2+ shows a reversible oxidation at E 1/2 = +1.16 V vs. ferrocene-ferrocenium. Coulometry confirms this oxidation to be a one-electron process. Electrochemical or chemical oxidation of [Os([9]aneS3)2]2+ gives [Os([9]aneS3)2]3+ Which has been characterised by electronic and ESR spectroscopy. Reaction of [OsCl2(4-MeC6H4Pri)}2] with 2 molar equivalents of [9]aneS3 in MeOH followed by addition of NaBPh, affords the mixed-sandwich complex [Os(4-MeC6H4Pri)([9]aneS3)][BPh4]2 in 65% yield. The complex [Os(4-MeC6H4Pri)([9]aneS3)][BPh4]2.MeNO2 crystallises in the triclinic space group P1BAR, a = 11.5027(8), b = 13.8509(13), c = 18.3983(12) angstrom, alpha = 94.72(1), beta = 105.01(3), gamma = 91.28(1)-degrees and Z = 2. The crystal structure shows facial co-ordination of both [9]aneS3 and 4-MeC6H4Pri at octahedral Os(II). Interestingly, there is an unusual disorder of the trithia macrocycle with two enantiomers of [9]aneS3 being present in the crystal: the two forms of the macrocycle were successfully modelled. Reaction of [MH2(CO)(PPh3)3] with 1 molar equivalent of [9]aneS3 in the presence of NH4PF6 in refluxing acetone (M = Ru) or refluxing 2-methoxyethanol (M = Os) for 2 h under N2 gives [MH(CO)(PPh3)([9]aneS3)]PF6. The complex [OsH(CO)(PPh3)([9]aneS3)]PF6. 0.5CH2Cl2 crystallises in the monoclinic space group P2(1)/n (alt. P2(1)/c, no. 14) with a = 1 5.955(6), b = 21.929(9), c = 8.895(7) angstrom, beta = 96.69(8)-degrees and Z = 4. The structure shows octahedral Os(II) with [9]aneS, bound facially, Os-S(1) 2.377(3) (trans to CO), Os-S(4) 2.369(3) (trans to PPh3), Os-S(7) 2.402(3) (trans to H), Os-H 1.60(9), Os-P 2.3344(24) and Os-C 1.868(11) angstrom. The reactivity of [MH(CO)(PPh3)([9]aneS3)]+ with O2 and chlorinated solvents is discussed.
• Dinuclear thioether half-sandwich ruthenium(<scp>II</scp>) complexes of the types [{RuL′([9]aneS₃)}₂(µ-L)_n]²⁺(n= 1, L′= PPh₃; n= 2, L′= MeCN), [{Ru([9]aneS₃)}₂(µ-L)₂]²⁺and [{Ru([9]aneS₃)}₂(µ-L)₃]⁺with heterocyclic thioamides L ([9]aneS₃= 1,4,7-trithiacyclononane)
  作者：Claudia Landgrafe、William S. Sheldrick

  DOI：10.1039/dt9960000989

  日期：——

  Reaction of [Ru(MeCN)(3)([9]aneS(3)-KAPPA(3)S)][CF3SO3](2)([9]aneS(3)=1,4,7-trithiacyclononane) with 1,3-benzothiazol-2-thione (Hbtt) and pyridine-2-thione (Hpyt) in methanol in a 1:1 molar ratio afforded dinuclear complexes [Ru([9]aneS(3)-KAPPA(3)S)}(2)(mu-L)(2)][CF3SO3](2) (L=btt or pyt) in which the ligands exhibit a tridentate mu-1KAPPAS:2KAPPA(2)N,S bridging mode. Crystallization of the btt complex from acetonitrile yielded [Ru(MeCN)([9]aneS(3)-KAPPA(3)S)}(2)(mu-btt)(2)][CF3SO3](2) with mu-S bridging ligands. A triply mu-S bridged complex [Ru([9]aneS(3)-KAPPA(3)S)}(2)(mu-btt)(3)][CF3SO3] was obtained from [Ru(MeCN)(3)([9]aneS(3)-KAPPA(3)S)][CF3SO3](2)and btt(-) in a 2:3 molar ratio. Fragments (Ph(3)P)([9]aneS(3)-KAPPA(3)S)Ru-II can be bridged with tetra- or tri-dentate dtuc(2-) (H(2)dtuc=2,4-dithiouracil) anions in [Ru(PPh(3))([9]aneS(3)-KAPPA(3)S)}(2)(mu-dtuc)](2+) and [RuCl(PPh(3))([9]aneS(3)-KAPPA(3)S)}(mu-dtuc)Ru(PPh(3))([9]aneS(3)-KAPPA(3)S)}](+). The structures of four complexes have been determined by X-ray crystallography.