(η-9-SMe2-7,8-Me2-7,8-C2B9H8)RhBr2 | 1441048-37-8

• 英文名称: (η-9-SMe2-7,8-Me2-7,8-C2B9H8)RhBr2
• 英文别名: (η-9-SMe₂-7,8-Me₂-7,8-C₂B₉H₈)RhBr₂
• CAS: 1441048-37-8
• 化学式: C₆H₂₀B₉Br₂RhS
• 分子量: 484.303
• InChiKey: CBQWKFYRUROGBN-SKSSAGQDSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Tl[Tl(η-7,8-C₂B₉H₁₁)] 、 (η-9-SMe2-7,8-Me2-7,8-C2B9H8)RhBr2 以 乙腈 为溶剂， 以77%的产率得到
  参考文献：
  名称：

  Rhoda- and iridacarborane halide complexes (η-9-SMe2-7,8-Me2-7,8-C2B9H8)MX2 (M = Rh, Ir; X = Cl, Br, I)

  摘要：

  Reaction of (eta-9-SMe2-7,8-Me-2-7,8-C2B9H8)M(cod) with hydrohalic acids affords the 16-valence-electron complexes (eta-9-SMe2-7,8-Me-2-7,8-C2B9H8)MX2 (M = Rh, X = Cl (3a), Br (3b), I (3c); M = Ir, X = Cl (4a), Br (4b), I (4c)). According to X-ray analysis, 3a, 3b, 4b, and 4c have monomeric pseudocloso-structures with a long cage C center dot center dot center dot C distance (2.122, 1.985, 2.238, and 2.186 angstrom, respectively), in contrast to dimeric closo-structures of the cage-non-methylated analogs. The structural difference was explained using DFT calculations. 3b and 4b react with SMe2 and Tl[Tl(eta-7,8-C2B9H11)] giving closo-metallacarboranes (eta-9-SMe2-7,8-Me-2-7,8-C2B9H8) M(SMe2)Br-2 (M = Rh (5), Ir (6)) and (h-9-SMe2-7,8-Me-2-7,8-C2B9H8) M(h-7,8-C2B9H11) (M = Rh (7), Ir (8)). (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.04.011
• 作为产物：
  描述：

  、 氢溴酸 在 乙酸酐 作用下， 以 水 为溶剂， 反应 2.0h， 以95%的产率得到(η-9-SMe2-7,8-Me2-7,8-C2B9H8)RhBr2
  参考文献：
  名称：

  Rhoda- and iridacarborane halide complexes (η-9-SMe2-7,8-Me2-7,8-C2B9H8)MX2 (M = Rh, Ir; X = Cl, Br, I)

  摘要：

  Reaction of (eta-9-SMe2-7,8-Me-2-7,8-C2B9H8)M(cod) with hydrohalic acids affords the 16-valence-electron complexes (eta-9-SMe2-7,8-Me-2-7,8-C2B9H8)MX2 (M = Rh, X = Cl (3a), Br (3b), I (3c); M = Ir, X = Cl (4a), Br (4b), I (4c)). According to X-ray analysis, 3a, 3b, 4b, and 4c have monomeric pseudocloso-structures with a long cage C center dot center dot center dot C distance (2.122, 1.985, 2.238, and 2.186 angstrom, respectively), in contrast to dimeric closo-structures of the cage-non-methylated analogs. The structural difference was explained using DFT calculations. 3b and 4b react with SMe2 and Tl[Tl(eta-7,8-C2B9H11)] giving closo-metallacarboranes (eta-9-SMe2-7,8-Me-2-7,8-C2B9H8) M(SMe2)Br-2 (M = Rh (5), Ir (6)) and (h-9-SMe2-7,8-Me-2-7,8-C2B9H8) M(h-7,8-C2B9H11) (M = Rh (7), Ir (8)). (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.04.011

文献信息

• Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence
  作者：Mikhail M. Vinogradov、Yulia V. Nelyubina、Dmitry A. Loginov、Alexander R. Kudinov

  DOI：10.1016/j.jorganchem.2015.04.007

  日期：2015.12

  Room temperature reactions of the rhodium and iridium bromides (eta-9-SMe2-7,8-Me-2-7,8-C2B9H8)MBr2 (M = Rh (1a), Ir (1b)) with CpTl give the dicarbollide thioether complexes (eta-9-SMe-7,8-Me-2-7,8-C2B9H8) MCp (2a,b), as a result of demethylation of the SMe2 substituent. These reactions are accompanied by transformation of cage structure from pseudocloso to closo. Refluxing of the sulfonium derivatives [(eta-9-SMe2-7,8-Me-2-7,8-C2B9H8)MCp](+) (3a,b) with [Bu4N]Br also affords 2a,b. In the same manner ruthenacarboranes [(eta-9-SMe2-7,8-C2B9H10)Ru(eta-C6H6)](+) (4a) and [(eta-10-SMe2-7,8-C2B9H10)Ru(eta-C6H6)](+) (4b) react with halide ions giving the thioether complexes (eta-9-SMe-7,8-C2B9H10)Ru(eta-C6H6) (5a) and (eta-10-SMe-7,8-C2B9H10)Ru(eta-C6H6) (5b). Dependence of the demethylation rate on the nature of halide ion and solvent was studied both experimentally and theoretically. The structures of 2a and 3aPF(6) were determined by X-ray diffraction. (C) 2015 Elsevier B.V. All rights reserved.