[Cp*Ir(III)(NO3)2] | 402824-54-8

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: [Cp*Ir(III)(NO3)2]
• 英文别名: (η5-C5Me5)Ir(η2-NO3)(η1-NO3)；[(η5-C5(CH3)5)Ir(III)(NO3)2]；[Cp(*)Ir(NO3)2]；iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;dinitrate
• CAS: 402824-54-8
• 化学式: C₁₀H₁₅IrN₂O₆
• 分子量: 451.459
• InChiKey: CICKPUPSDSWGMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.47
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  126
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [Cp*Ir(III)(NO3)2] 、 [Ni(TsTACN-S2)] 以 甲醇 为溶剂， 反应 5.0h， 以94%的产率得到[(η⁵-penta-methylcyclopentadienyl)Ir(NO₃)Ni(1,4-bis(2-mercaptoethyl)-7-tosyl-1,4,7-triazacyclononane)]NO₃
  参考文献：
  名称：

  N 3 S 2 桥联配体负载的双核Ni II Ir III氢化物配合物的合成和结构：在水性介质中双核Ni II（μ- H）M III单元（M = Rh，Ir）的性质和反应性的比较

  摘要：

  水溶性双核镍II铱III复合物与桥接氢化物，混合[Cp *的Ir（μ -H）的Ni（TsTACN（C 2 H ^ 4 S）2）] NO 3（TsTACN（C 2 H ^ 4 SH）2  = 1,4-双（2-巯基乙基）-7-甲苯磺酰基-1,4,7-三氮杂中，Cp * =  η 5 -五甲基环戊二烯基，[图2b ] NO 3，其通过双核镍反应来合成），II铱III络合物[Cp * Ir（NO 3）Ni（TsTACN（C 2 H 4 S）2）] NO 3（[ 1b ] NO 3）与HCOONa的水溶液。通过X射线分析明确确定[ 2b ] NO 3的结构，以便将其在水性介质中的结构，性质和反应性与相应的铑对应物[Cp * Rh（μ- H）Ni（TsTACN） （C 2 H 4 S）2）] NO 3（[ 2a ] NO 3）。Ni⋯Ir距离（av.2.721Å）比Ni⋯Rh间隔（av.2.691Å）稍长。Ni

  DOI：

  10.1016/j.jorganchem.2013.03.005
• 作为产物：
  描述：

  [(η5-C5(CH3)5)Ir(III))2(μ-H)3]NO3 、 硝酸 以 硝酸 为溶剂， 生成 [Cp*Ir(III)(NO3)2]
  参考文献：
  名称：

  pH-Dependent H₂-Activation Cycle Coupled to Reduction of Nitrate Ion by Cp*Ir Complexes

  摘要：

  This paper reports a pH-dependent H-2-activation {H-2 (pH 1-4) --> H+ + H- (pH -1) --> 2H(+) + 2e(-)} promoted by Cp*Ir complexes {Cp* = eta(5)-C-5(CH3)(5)}. In a pH range of about 1-4, an aqueous HNO3 solution of [Cp*Ir-III(H2O)(3)](2+) (1) reacts with 3 equiv of H-2 to yield a solution of [(Cp*Ir-III)(2)(mu-H)(3)](+) (2) as a result of heterolytic H-2-activation {2[1] + 3H(2) (pH 1-4) --> [2] + 3H(+) + 6H(2)O}. The hydrido ligands of 2 display protonic behavior and undergo H/D exchange with D+: [M-(H)(3)-M](+) + 3D(+) reversible arrow [M-(D)(3)-M](+) + 3H(+) (where M = Cp*Ir). Complex 2 is insoluble in a pH range of about -0.2 (1.6 M HNO3/H2O) to -0.8 (6.3 M HNO3/H2O). At pH -1 (10 M HNO3/H2O), a powder of 2 drastically reacts with HNO3 to give a solution of [Cp*Ir-III(NO3)(2)] (3) with evolution of H-2, NO, and NO2 gases. D-labeling experiments show that the evolved H-2 is derived from the hydrido ligands of 2. These results suggest that oxidation of the hydrido ligands of 2 {[2] + 4NO(3)(-) (pH -1) --> 2[3] + H-2 + H+ + 4e(-)} couples to reduction of NO3- (NO3- --> NO2- --> NO). To complete the reaction cycle, complex 3 is transformed into 1 by increasing the pH of the solution from -1 to 1. Therefore, we are able to repeat the reaction cycle using 1, H-2, and a pH gradient between 1 and -1. A conceivable mechanism for the H-2-activation cycle with reduction of NO3- is proposed.

  DOI：

  10.1021/ja011846l

文献信息

• Systematic Heterodinuclear Complexes with MM′(μ-meppp) Centers That Tune the Properties of a Nesting Hydride (M = Ni, Pd, Pt; M′ = Rh, Ir; H₂meppp = <i>meso</i>-1,3-Bis[(mercaptoethyl)phenylphosphino]propane)
  作者：Bunsho Kure、Mikie Sano、Takayuki Nakajima、Tomoaki Tanase

  DOI：10.1021/om500410f

  日期：2014.8.11

  and PtIIRhIII ([6c]NO3) complexes, the hydrides were extremely unstable and were likely to undergo an unusual metal-to-Cp* ring hydrogen transfer, resulting in η4-C5Me5H MIIRhI complexes, [M(μ-meppp)Rh(η4-C5Me5H)]NO3 (M = Pd ([7b]NO3), Pt ([7c]NO3)). The property of the hydride was drastically switched by varying the anchoring metal ions of the M′ site (Rh, Ir); that of [6a]NO3 (M′ = Rh) is not protic

  具有P 2 S 2配体[M（meppp）]（M = Ni（1a），Pd（1b），Pt（1c）； H 2 meppp =中观-1,3-双[（巯基乙基）苯基膦基]丙烷），用[* M'CP氯处理2 ] 2或[M'CP *（NO 3）2 ]（CP * =η 5 -五甲基），得到一系列bisthiolate桥连中号II M' III异核复合物，[M（μ-meppp）M'CP * X] X'（M = Ni，Pd，Pt; M'= Rh，Ir; X = Cl，NO 3 ; X'= Cl，PF 6，NO 3）。硝酸盐络合物[M（μ-meppp）-M'CP *（NO 3）] NO 3（M'= Rh（[ 4a – c ] NO 3），Ir（[ 5a – c ] NO 3）; M = Ni（a），Pd（b），Pt（c））进一步与甲酸钠在水或甲醇中反应，转化为双硫醇盐和氢化物桥接的配合物[M（μ-meppp）（μ-H）M'
• A New Water-soluble and Acid-stable Dinuclear Organoiridium Dinitrate Complex
  作者：Bunsho Kure、Shunichi Fukuzumi、Seiji Ogo

  DOI：10.1246/cl.2007.1468

  日期：2007.12.5

  A new water-soluble and acid-stable dinuclear organoiridium(III) dinitrate complex [Cp∗Ir(NO3)}2(μ-Cl)2] (1, Cp∗ = η5-C5Me5) was synthesized by the reaction of a water-insoluble organoiridium(III) complex [(Cp∗IrCl)2(μ-Cl)2] (2) with two equivalents of AgBF4 in aqueous nitric acid (1 M HNO3/H2O) at 23 °C for 12 h. The structure of 1 with two monodentate NO3− ligands is discussed in comparison with structure of a mononuclear organoiridium(III) complex with one monodentate and one bidentate NO3− ligands, [Cp∗Ir(NO3)2] (3).

  一种新型水溶性和耐酸的二核有机铱(III)硝酸盐配合物 [Cp∗Ir(NO3)}2(μ-Cl)2] (1, Cp∗ = η5-C5Me5) 是通过将一种水不溶性有机铱(III)配合物 [(Cp∗IrCl)2(μ-Cl)2] (2) 与两等量的 AgBF4 在水相硝酸中 (1 M H /H2O) 反应 12 小时合成的，反应温度为 23 °C。文章还讨论了 1 的结构，其中包含两个单齿 − 配体，并与一种一核有机铱(III) 配合物 [Cp∗Ir( )2] (3) 的结构进行了比较，该配合物含有一个单齿和一个双齿 − 配体。
• (η⁵-Pentamethylcyclopentadienyl)rhodium and -iridium Complexes with Weakly and Strongly Coordinating Anions:  Isolation and First X-ray Molecular Structures of the Tris(solvent) Complexes [(C₅Me₅)M(acetone)₂(H₂O)][BF₄]₂ (M = Rh, Ir)
  作者：Hani Amouri、Carine Guyard-Duhayon、Jacqueline Vaissermann、Marie Noelle Rager

  DOI：10.1021/ic010772b

  日期：2002.3.1

  Several novel pentamethylcyclopentadienyl complexes of general formula [(C5Me5)IrL3][BF4]2 were prepared including the tris(solvent) precursors [(C5Me5)M(acetone)2(H2O)][BF4]2 (M = Rh, Ir) (1a,b). The X-ray molecular structures of 1a,b were determined at low temperature. Complexes 1a,b are isostructural, and both compounds crystallize in the monoclinic space group P2(1)/c with a = 10.157(3) A, b =

  制备了几种新颖的通式[（C5Me5）IrL3] [ ] 2的五甲基环戊二烯基配合物，包括三（溶剂）前体[（C5Me5）M（丙酮）2（H2O）] [ ] 2（M = Rh，Ir） （1a，b）。在低温下确定1a，b的X射线分子结构。配合物1a，b是同构的，两种化合物在单斜空间群P2（1）/ c中均以a = 10.157（3）A，b = 14.038（9）A，c = 16.335（2）A，β= 99.73结晶。 （2）度，对于1a且Z = 4，a = 10.107（9）A，b = 13.994（16）A，c = 15.996（34）A，β= 99.61（12）度，对于Z = 4 1b。配位的水分子氢键合到两个BF4（-）阴离子上。1a，b与吡啶（py）反应得到相关的三（吡啶）配合物[（C5Me5）M（eta1-（N）-py）3] [ ] 2（M = Rh，Ir）（2a，b） 。配合