[(η5-C5(CH3)5)Ir(III))2(μ-H)3]NO3 | 402824-52-6

• 英文名称: [(η5-C5(CH3)5)Ir(III))2(μ-H)3]NO3
• 英文别名: [(Cp*Ir(III))2(μ-H)3]NO3
• CAS: 402824-52-6
• 化学式: C₂₀H₃₃Ir₂*NO₃
• 分子量: 719.927
• InChiKey: ADOQBSFBFUDZKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  [(η5-C5(CH3)5)Ir(III))2(μ-(2)H)3]NO3 、 硝酸 以 硝酸 为溶剂， 生成 [(η5-C5(CH3)5)Ir(III))2(μ-H)3]NO3
  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

• H₂-Initiated Reversible Switching between Two-Dimensional Metallacycles and Three-Dimensional Cylinders
  作者：Ying-Feng Han、Long Zhang、Lin-Hong Weng、Guo-Xin Jin

  DOI：10.1021/ja508543y

  日期：2014.10.15

  solution that can be accomplished by uptake or release of H2. An efficient route for synthesizing air- and moisture-stable 16-electron M2L2-type metallacycles under very mild conditions has been developed. The new organometallic metallacycles favor the binding of small ligands such as MeCN, Cl(-), CO, and pyridine. The reaction of a coordinatively unsaturated 16-electron M2L2-type macrocyclic complex featuring

  尽管过渡金属络合物对分子氢 (H2) 的可逆共价活化是一种常见反应，但尚未描述 H2 介导的有机金属框架的复杂可逆排列。在这里，我们报告了溶液中不寻常的有机金属转化，可以通过吸收或释放 H2 来实现。已经开发出一种在非常温和的条件下合成空气和水分稳定的 16 电子 M2L2 型金属环的有效途径。新的有机金属金属环有利于小配体如 MeCN、Cl(-)、CO 和吡啶的结合。以硫酮配体为特征的配位不饱和 16 电子 M2L2 型大环配合物与 1 个大气压的 H2 的反应导致 18 电子 M2L3 型圆柱体以及氢化物物种的分离。值得注意的是，所获得的混合物在加热时以容易的方式失去H2以重新形成起始的M2L2型复合物。提出了可逆转换的可能机制。