| 1441048-24-3

• CAS: 1441048-24-3
• 化学式: C₁₄H₃₂B₉IrS
• 分子量: 521.993
• InChiKey: UQRFZSKTEFHZGC-GCOBPYNFSA-N

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：

  以 1,2-二氯乙烷 为溶剂， 反应 3.0h， 以92%的产率得到1,8-Me₂-2,2-(cod)-7-SMe₂-2,1,8-closo-IrC₂B₉H₈
  参考文献：
  名称：

  铑和铱与异碳硼烷阴离子[7,8-Me2-X-SMe2-7,8-nido-C2B9H8]-的多面体重排（X = 9和10）

  摘要：

  Polyhedral rearrangement of iridacarborane 1,2-Me-2-3,3-(cod)-4-SMe2-3,1,2-closo-IrC2B9H8 (1) proceeds in a solution at RT and affords a product of 1,2 -> 1,7 isomerization 1,8-Me-2-2,2-(cod)-7-SMe2-2,1,8-closo-IrC2B9H8 (2). Rhodium derivative 1,2-Me-2-3,3-(cod)-4-SMe2-3,1,2-closo-RhC2B9H8 (3) is significantly more stable toward heating than iridium complex 1 and isomerizes at 110 degrees C by 1,2 -> 1,2 and 1,2 -> 1,7 reaction schemes with 1,2 -> 1,2 being the predominant route forming 1,2-Me-2-4,4-(cod)-8-SMe2-4,1,2-closo-RhC2B9H8 (4) and 1,8-Me-2-2,2-(cod)-7-SMe2-2,1,8-closo-RhC2B9H8 (5). Complexes 4 and 5 were characterized by B-11{H-1}-B-11{H-1} COSY NMR spectrometry. A mechanism of 1,2 -> 1,2 isomerization of 3 to 4 was proposed on the basis of DFT calculations. Reaction of the thallium salt Tl[7,8-Me-2-9-SMe2-7,8-nido-C2B9H8] (CarbTl) with [Cp*RuCl](4) in THE furnishes new ruthenacarborane 1,2-Me-2-3-(Cp*)-4-SMe2-3,1,2-closo-RuC2B9H8 (6). Heating of 6 at 80 and 144 degrees C leads to the partial and complete decomposition, respectively. Interaction of CarbTl with [Cp*IrCl2](2) in the presence of TlPF6 provides two new Ir(III) complexes [1,2-Me-2-3-(Cp*)-4-SMe2-3,1,2-closo-IrC2B9H8]PF6 (7PF(6)) and 1,2-Me-2-3-(Cp*)-4-SMe-3,1,2-closo-IrC2B9H8 (8) both stable upon heating in boiling tetrachloroethane.(146 degrees C). A new 10-substituted charge-compensated carborane [7,8-Me-2-10-SMe2-7,8-nido-C2B9H9] (9) was synthesized via an interaction of dicarbollide dianion [7,8-Me-2-7,8-nido-C2B9H9](2-) with dimethyl sulfide and acetaldehyde in acidic media. Thallium salt of 9 Tl[7,8-Me-2-10-SMe2-7,8-nido-C2B9H8] (10) reacts with [(cod)IrCl](2) furnishing positional isomer of 1 with a symmetrical emplacement of SMe2 substituent complex 1,2-Me-2-3,3-(cod)-8-SMe2-3,1,2-closo-IrC2B9H8 (11). Iridacarborane 11 requires elevated temperatures to undergo cage isomerization and converts upon heating at 110 degrees C to two new compounds 1,8-Me-2-2,2-(cod)-11-SMe2-2,1,8-closo-IrC2B9H8 (12) and 1,2-Me-2-4,4-(cod)-9-SMe2-4,1,2-closo-IrC2B9H8 (13) as a result of 1,2 -> 1,7 and 1,2 -> 1,2 rearrangements respectively with 13 being the minor product. The structures of 2, 6, 7PF(6), 8, 10, 12, and 13 were determined by single-crystal X-ray diffraction.

  DOI：

  10.1021/acs.organomet.6b00858
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 Tl[9-SMe₂-7,8-Me₂-7,8-C₂B₉H₈] 以 四氢呋喃 为溶剂， 以73%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