η5-pentamethylcyclopentadienyl-[1,2-dicarba-closo-dodecaborane(12)-diselenolato]iridium | 226222-94-2

• 英文名称: η5-pentamethylcyclopentadienyl-[1,2-dicarba-closo-dodecaborane(12)-diselenolato]iridium
• 英文别名: pentamethylcyclopentadienyl-(1,2-dicarba-closo-dodecaborane-1,2-diselenolato)iridium；Cp*Ir[Se2C2(B10H10)]；[η5-C5(CH3)5Ir(1,2-dicarba-closo-dodecaborane-1,2-diselenolate)]；[(η5-pentamethylcyclopentadienyl)Ir(Se2C2B10H10)]；[(η5-C5Me5Ir(ortho-carborane-1,2-diselenolato)]；(η5-C5Me5)Ir[Se2C2(B10H10)]
• CAS: 226222-94-2
• 化学式: C₁₂H₂₅B₁₀IrSe₂
• 分子量: 627.58
• InChiKey: SKKYGXLDELZTHM-UHFFFAOYSA-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：

  η5-pentamethylcyclopentadienyl-[1,2-dicarba-closo-dodecaborane(12)-diselenolato]iridium 、 iron pentacarbonyl 在 (CH₃)3NO 作用下， 以 甲苯 为溶剂， 以56%的产率得到[η5-pentamethylcyclopentadienyl-[1,2-dicarba-closo-dodecaborane(12)-diselenolato]iridium][(Fe(CO)3)]
  参考文献：
  名称：

  Synthesis and Structure of Heterometallic Clusters (IrCo₂, IrFe) Containing Bridging 1,2-Dicarba-closo-dodecaborane-1,2-dichalocogenolato Ligands

  摘要：

  The 16-electron half-sandwich iridium complexes [Cp*Ir{E2C2(B10H10)}] [E = S (1a), Se (1b)] (Cp* = eta(5)-C5Me5) [Cp*Ir[E2C2(B10H10)] = eta(5)-pentamethylcyclopentadienyl-[1,2-dicarbacloso-dodecaborane(12)-dichalcogenolato]iridium] reacted with Co-2(CO)(8) in toluene solution to afford the trinuclear clusters [Cp*Ir{E2C2(B10H10)}]{Co-2(CO)(5)} [E = S (2a), Se (2b)] and mononuclear complexes [Cp*Ir(CO){E2C2(B10H10)}] [E = S (3a), Se (3b)] as byproducts. Compounds 2a and 2b contain closed IrCo2 triangle geometry with one Co-Co and two Ir-Co bonds. The dinuclear IrFe complexes [Cp*Ir{E2C2(B10H10)}]{Fe(CO)(3)} [E = S (4a), Se (4b)] were obtained from the reactions of 1a and 1b with Fe(CO)5 in the presence of Me3NO. The molecular structures of 2a, 2b, and 4b have been determined by X-ray crystallography.

  DOI：

  10.1021/om049185z
• 作为产物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 dilithium 1,2-dicarba-closo-dodecaborane(12)-1,2-diselenolate 以 四氢呋喃 、 乙醚 为溶剂， 以91%的产率得到η5-pentamethylcyclopentadienyl-[1,2-dicarba-closo-dodecaborane(12)-diselenolato]iridium
  参考文献：
  名称：

  含有 1,2-Dicarba-closo-ddecaborane-1,2-diselenolato 配体的两种 Cp*Ir 半夹心配合物的 NMR 光谱和 X 射线晶体结构表征

  摘要：

  [Cp*IrCl2](2) 与 1,2-orthocarborane-1,2-diselenolate 3 反应生成绿色 16 电子二硒烯复合物 [Cp*Ir{Se2C2(B10H10)}] (4)双电子配体，如三甲基膦，得到 18 电子二硒化物衍生物 [Cp*Ir(PMe3)-{Se2C2(B10H10)}] (5)。4和5的分子结构通过X-射线晶体结构分析确定。与 5 相比，4 中的 Se-77-核屏蔽降低了近 500 ppm。

  DOI：

  10.1002/(sici)1099-0682(199905)1999:5<873::aid-ejic873>3.0.co;2-m

文献信息

• Synthesis and characterization of binuclear half-sandwich metal (Co, Ir and Ru) complexes containing ancillary ortho-carborane-1,2-dithiolato ligands
  作者：Shuang Liu、Jiasheng Zhang、Xin Wang、Guo-Xin Jin

  DOI：10.1039/b608934h

  日期：——

  The assembly of soluble, air-stable, binuclear structures, namely (p-cymene)Ru[S2C2(B10H10)]}2(µ-pyz) (4), Cp*Co[S2C2(B10H10)]}2(µ-pyz) (5), Cp*Co[S2C2(B10H10)]}2(µ-bpy) (6), Cp*Co[S2C2(B10H10)]}2(µ-bpe) (7) and Cp*Ir[E2C2(B10H10)]}2(µ-bpo) (E = S (8a), Se (8b)), in which organometallic units are bridged by pyridyl-based organic linkers, are synthesized. The complexes have been fully characterized by IR and NMR spectroscopy, as well as elemental analysis. The molecular structures of 4, 5, 6, 7 and 8 are established through X-ray crystallography.

  通过有机配体吡啶基连接的金属有机单元，合成了可溶、空气稳定的二核结构，即(p-cymene)Ru[S2C2(B10H10)]}2(µ-pyz) (4), Cp*Co[S2C2(B10H10)]}2(µ-pyz) (5), Cp*Co[S2C2(B10H10)]}2(µ-bpy) (6), Cp*Co[S2C2(B10H10)]}2(µ-bpe) (7) 及 Cp*Ir[E2C2(B10H10)]}2(µ-bpo) (E = S (8a), Se (8b)) 等化合物。这些配合物已通过红外、核磁共振谱以及元素分析得到充分表征。通过X射线晶体学确定了4、5、6、7、8的分子结构。
• Synthesis and Characterization of Binuclear Half-Sandwich Iridium and Rhodium Carbene Complexes Containing 1,2-Dichalcogenolato Carborane or Carbonato Ligands
  作者：Wei-Guo Jia、Ying-Feng Han、Guo-Xin Jin

  DOI：10.1021/om800694h

  日期：2008.11.24

  Reactions of bi-NHC ligands with the 16-electron half-sandwich Ir and Rh dichalcogenolato carborane complexes Cp*M[E2C2(B10H10)] (M = Ir, Rh; E = S, Se) or 16-electron half-sandwich Ir and Rh carbonate complexes Cp*M(μ-O)2CO (M = Ir, Rh) give corresponding 18-electron binuclear complexes of the type [Cp*M(E2C2(B10H10))}2L] (L = 1,1′-(1,2-ethanediyl)bis(3-methylimidazolin-2-ylidene); M = Ir, E = S

  双-NHC配体与16电子半夹心式Ir和Rh二卤代原烟酸酯碳硼烷络合物Cp * M [E 2 C 2（B 10 H 10）]（M = Ir，Rh; E = S，Se）或16的反应-电子半三明治式Ir和Rh碳酸盐复合物Cp * M（μ-O）2 CO（M = Ir，Rh）得到相应的18电子双核复合物，类型为[Cp * M（E 2 C 2（B 10 H 10））} 2 L]（L = 1,1'-（1,2-乙二基）双（3-甲基咪唑啉-2-亚基）； M = Ir，E = S（4a），Se（4b）； M = Rh，E = S（5a），Se（5b））和[Cp * M（μ-O）2CO] 2 L（M = Ir（8），Rh（9））。配合物4 - 9也可以从混合[Cp *的MC1的反应直接得到2 ] 2 L（M =铱（2），铑（3））与Li 2 [E 2 Ç 2（B 10 H ^ 10）]或Na 2 CO 3高收
• Metal-induced BH activation. Addition of phenylacetylene to Cp*Rh-, Cp*Ir-, (p-cymene)Ru- and (p-cymene)Os halfsandwich complexes containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligand
  作者：Max Herberhold*、Hong Yan、Wolfgang Milius、Bernd Wrackmeyer*

  DOI：10.1016/s0022-328x(00)00221-7

  日期：2000.6

  The addition reactions of the 16e halfsandwich complexes Cp*M[S2C2(B10H10)] (1S M=Rh, 2S M=Ir) and η6-(4-isopropyltoluene)M[S2C2(B10H10)] (3S M=Ru and 4S M=Os) with phenylacetylene lead selectively to the 18e complexes 5S–8S, in which a metalboron bond is present and the phenylacetylene is regio- and stereoselectively inserted into one of the MS bonds, with one hydrogen atom transferred from the

  halfsandwich络合物的Cp * M [S的16E的加成反应2 Ç 2（B 10 H ^ 10）]（1S M = RH，2S M = Ir）的和η 6 - （4- isopropyltoluene）M [S 2 Ç 2（ B 10 H 10）]（3S M = Ru和4S M = Os）与苯乙炔选择性地引入18e络合物5S – 8S，其中存在金属硼键，苯乙炔在区域选择性和立体选择性地插入一个MS键，一个氢原子从碳硼烷笼转移到炔烃的末端碳，与原金属化相对应碳硼烷的笼子。在所有情况下，S-η 2 - （PH）CC和C（1）B单元被链接到在金属cisoid位置。Cp * Ir [Se 2 C 2（B 10 H 10）] 2Se与苯乙炔的类似反应得到6Se。配合物5S在溶液中发生分子内重排，形成异构体9S在RhB键断裂的情况下，现在带有有机取代基的B原子和金属碳σ键与配位的S→Rh键一起形成。与此相反，p
• Synthesis and characterization of half-sandwich iridium complexes containing 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene and ancillary ortho-carborane-1,2-dichalcogenolato ligands
  作者：Ying-Feng Han、Jia-Sheng Zhang、Yue-Jian Lin、Jie Dai、Guo-Xin Jin

  DOI：10.1016/j.jorganchem.2007.04.034

  日期：2007.10

  iridium complexes Cp∗IrCl2}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (3) and Cp∗Ir[E2C2(B10H10)]}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (E = S(5a), Se(5b)) were prepared from the reaction of [Cp∗IrCl(μ-Cl)]2 or the “pseudo-aromatic” half-sandwich iridium complex Cp∗Ir[E2C2(B10H10)] (E = S(4a), Se(4b)) with a tetrathiafulvalene (TTF) derivative 2,6-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene

  双核半三明治铱络合物Cp ∗ IrCl 2 } 2（μ-2,6（7）-双（4-吡啶基）-1,4,5,8-四硫富瓦烯）（3）和Cp ∗ Ir [ E 2 C 2（B 10 H 10）]}} 2（μ-2,6（7）-双（4-吡啶基）-1,4,5,8-四硫富瓦烯）（E = S（5a），Se（5b））是由[Cp * IrCl（μ-Cl）] 2或“拟芳族”半三明治铱络合物Cp * Ir [E 2 C 2（B 10 H 10）]（E = S（4a），Se（4b））和四硫富瓦烯（TTF）衍生物2,6-双（4-吡啶基）-1,4,5,8-四硫富瓦烯（2）在室温下。配合物（3，图5a和图5b）已经被充分表征通过IR和NMR光谱，以及元素分析。通过X射线晶体学建立了2和5a的分子结构。有趣的是，无限的隧道是通过重复5a的“屈曲碗”分子而创建的。
• Addition of ethynylferrocene to transition-metal complexes containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligand—in vitro cooperativity of a ruthenium compound on cellular uptake of an anticancer drug
  作者：De-Hong Wu、Chun-Hui Wu、Yi-Zhi Li、Da-Dong Guo、Xue-Mei Wang、Hong Yan

  DOI：10.1039/b810831e

  日期：——

  The addition reactions of the 16e half-sandwich complexes (p-cymene)M(S2C2B10H10) (1S, M = Ru; 2S, M = Os) and Cp*Ir(E2C2B10H10) (3S, E = S; 3Se, E = Se) with ethynylferrocene lead selectively to the 18e complexes (p-cymene)Ru(S2C2B10H9)(H2CCFc) (Fc = ferrocenyl) (4S), (p-cymene)Os(S2C2B10H9)(H2CCFc) (5S), Cp*Ir(S2C2B10H9)(H2CCFc) (6S) and Cp*Ir(Se2C2B10H9)(H2CCFc) (6Se), in which the alkyne is regio- and stereoselectively inserted into one of the M–E bonds that may further lead to metal-induced B–H activation, hydrogen atom transfer from the carboranevia the metal center to the inserted alkyne, and the generation of a M–B bond. In all complexes the S-η2-(Fc)C–C and C–B(M) moieties occupy a cisoid position. The four new complexes are characterized by IR, MS, NMR spectroscopy and microanalysis, and the X-ray structural analysis of 4S is performed. 4S was observed to promote the uptake of anticancer drug daunorubicin in drug-resistant leukemia K562 cells.

  16e 半夹心配合物 (p-cymene)M(S2C2B10H10) (1S, M = Ru; 2S, M = Os) 和 Cp*Ir(E2C2B10H10) (3S, E = S.; 3Se, E = Se) 与二茂铁乙炔的加成反应，选择性地生成了 18e 配合物 (p-cymene)Ru(S2C2B10H9)(H2CCFc) (F.) ；3Se，E = Se）与二茂铁乙炔的反应，选择性地生成 18e 复合物 (对二茂铁)Ru(S2C2B10H9)(H2CCFc) (Fc = 二茂铁基) (4S)、(p-cymene)Os(S2C2B10H9)(H2CCFc) (5S)、Cp*Ir(S2C2B10H9)(H2CCFc) (6S) 和 Cp*Ir(SE2C2B10H9)(H2CCFc) (6Se)、在这些复合物中，炔烃具有区域和立体选择性地插入到一个 MâE 键中，这可能会进一步导致金属诱导的 BâH 活化、氢原子从金属中心的碳环转移到插入的炔烃，并生成一个 MâB 键。在所有配合物中，S-Î-2-（Fc）CâC 和 CâB(M) 分子均占据顺式位置。研究人员通过红外光谱、质谱、核磁共振光谱和显微分析对这四种新复合物进行了表征，并对 4S 进行了 X 射线结构分析。研究观察到 4S 能促进耐药性白血病 K562 细胞对抗癌药物 daunorubicin 的吸收。