(hydridotris(3,5-dimethylpyrazolyl)borate)Ir(C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me))(acetonitrile) | 501330-72-9

• 英文名称: (hydridotris(3,5-dimethylpyrazolyl)borate)Ir(C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me))(acetonitrile)
• 英文别名: (hydrotris(3,5-dimethylpyrazolyl)borato)Ir(C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me))(acetonitrile)；Tp(Me2)Ir(C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me))(NCMe)
• CAS: 501330-72-9
• 化学式: C₃₅H₄₃BIrN₇O₁₂
• 分子量: 956.797
• InChiKey: WTSUBCDWEWSXNX-JRYLAINFSA-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

• 作为产物：
  描述：

  (hydrotris(3,5-dimethylpyrazolyl)borato)Ir(C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me))(H2O)*(dichloromethane) 、 乙腈 以 乙腈 为溶剂， 生成 (hydridotris(3,5-dimethylpyrazolyl)borate)Ir(C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me)C(CO2Me)=C(CO2Me))(acetonitrile)
  参考文献：
  名称：

  铱的金属杂环庚烯（III）：合成与反应性

  摘要：

  红外（I）丁二烯络合物TP ME2的Ir（η 4 -CH 2 C（Me）的C（Me）的CH 2）（1）（TP ME2 =氢三（3,5-二甲基）硼酸盐）反应以≥3当量DMAD（RC⋮CR，R = CO 2 Me）在CH 2 Cl 2中，在不定水存在下，在60°C下通过三个DMAD分子的氧化偶联形成iridacycloheptatriene （2）金属配位球。在相关过程中，Tp Me2 IrPh 2（N 2）（4）给出两个苯甲酰化的iridacycloheptatrienes，对称的物种（5）和不对称的物种（6）。这些络合物中的水配体不稳定，并且已经获得了被CO，PMe 3和NCMe取代的衍生物。2，5，和6的反应，在25℃下，用氧代传递的氧化剂如吨BuOOH与形成酮基metallabicyclic产品7 - 9，从选择性氧代攻击的γ，δ-C，其导致Ç双键，无论其是苯甲酸酯型还是（R）C C（

  DOI：

  10.1021/om061036o

文献信息

• Coupling of Internal Alkynes in Tp^Me2Ir Derivatives:  Selective Oxidation of a Noncoordinated Double Bond of the Resulting Iridacycloheptatrienes
  作者：Eleuterio Álvarez、Margarita Gómez、Margarita Paneque、Cristina M. Posadas、Manuel L. Poveda、Nuria Rendón、Laura L. Santos、Susana Rojas-Lima、Verónica Salazar、Kurt Mereiter、Caridad Ruiz

  DOI：10.1021/ja0290375

  日期：2003.2.1

  The reaction of different Tp(Me2)Ir derivatives and dimethylacetylene dicarboxylate (DMAD) allows the preparation of three different metallacycloheptatriene complexes and an unusual allyl-terminated metallacycle. The C atoms of distant C=C bonds in the metallacycles, including aromatic ones, can be converted selectively to the corresponding keto functionality under mild conditions.
• Reactivity of the Iridium(I) Alkene/Alkyne Complex Tp^Me2Ir(C₂H₄)(MeO₂CC⋮CCO₂Me)
  作者：Margarita Paneque、Cristina M. Posadas、Manuel L. Poveda、Nuria Rendón、Kurt Mereiter

  DOI：10.1021/om061056q

  日期：2007.6.1

  Tp(Me2)Ir(C2H4)(2) ( 1; Tp(Me2)) hydrotris(3,5-dimethylpyrazolyl) borate) reacts with 1 equiv of MeO2CC=CCO2Me (DMAD) at 25 degrees C, via the intermediacy of the known Ir(I) adduct Tp(Me2)Ir(C2H4)( DMAD) ( 2), with formation of the bis( alkenyl) derivative Tp(Me2)Ir(cis-C( R) =C( R) H)(CH= CH2)(C2H4) ( 3; R = CO2Me) in ca. 50% yield. Complex 3 slowly evolves to another alkenyl species, Tp(Me2)Ir(cis-C( R)=C( R) H)(CH2CH2CH=CH2) ( 4), which exists as a mixture of two stereoisomers. Interestingly, complex 2 reacts with the hard Lewis base NCMe at - 20 degrees C, giving the Ir( I) adduct Tp(Me2)Ir( DMAD)( NCMe) ( 5) the first Ir( I) compound of the Tp(Me2)Ir system with a hard ligand. The Ir- NCMe bond in 5 is labile, and the acetonitrile is easily interchanged by CO, C2H4, and the alkynes HC=CCO2Me ( MP) and DMAD. While with CO the reaction stops at the substitution stage with formation of Tp(Me2)Ir(DMAD)( CO) ( 8), with C2H4 it gives complex 4 or the bis(alkenyl) species Tp(Me2)Ir(cis-C(R)= C(R) H)(CH=CH2)(NCMe) ( 9), depending on the concentration of NCMe in the reaction medium. With MP the known iridacyclopentadiene Tp(Me2)Ir(C(R)=C(H) C( R)=C( R))(NCMe) ( 10) and the symmetrical iridacycloheptatriene Tp(Me2)Ir(C( R)=C( H) C( R)=C( R) C( H)=C( R)( NCMe) (11) can be obtained, while related iridacycles are formed with DMAD. Finally an iridapyrrole with the composition Tp(Me2)Ir(Cl)(C(R)=C(R) C(Me)=NH) ( 6) is the unexpected result of heating complex 5 in a CH2Cl2NCMe mixture at 120 degrees C. All of the new compounds reported have been characterized by microanalysis and IR and NMR spectroscopy and, in addition, complexes 4 and 6 have been characterized by single-crystal X-ray studies.