(bis(bis(trifluoroethoxy)phospino)methylamine)3Ir2(I,III)H3Br | 830347-03-0

• 英文名称: (bis(bis(trifluoroethoxy)phospino)methylamine)3Ir2(I,III)H3Br
• CAS: 830347-03-0
• 化学式: C₂₇H₃₆BrF₃₆Ir₂N₃O₁₂P₆
• 分子量: 1928.72
• InChiKey: UEOYMNWQAMZNSZ-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  (bis(bis(trifluoroethoxy)phospino)methylamine)3Ir2(0,II)(neopentyl)Br 、 氢气 以 二氯甲烷 为溶剂， 以55%的产率得到(bis(bis(trifluoroethoxy)phospino)methylamine)3Ir2(I,III)H3Br
  参考文献：
  名称：

  Hydrogenation of Two-Electron Mixed-Valence Iridium Alkyl Complexes

  摘要：

  Two-electron mixed-valence complexes of the general formula (tfepma)(3)lr(2)(0)'(RBr)-R-ll [tfepma = bis(bis(trifluoroethoxy)-phosphino)methylamine, MeN[P(OCH2CF3)(2)](2), and R = CH3 (2), CH2C(CH3)(3) (3)] have been synthesized and structurally characterized and their reactivity with H-2 investigated. Hydrogenation of 2 and 3 proceeds in a cascade reaction to produce alkane upon initial H-2 addition, followed by the formation of the lr(2)(I,III) binuclear trihydridebromide complex (tfepma)(3)lr(2)(I,III)H(3)Br (4) upon the incorporation of a second molecule of H-2. Hydrogenation of two-electron mixed-valence di-iridium alkyl complexes is examined with nonlocal density-functional calculations. H-2 attacks the Ir-II metal center prior to alkyl protonation to produce an eta(2) -H-2 complex. Transition states link all intermediates to a complex that has the same regiochemistry as the crystallographically determined final product. Calculated atomic charges suggest that the second H-2 molecule is homolytically cleaved within the di-iridium coordination sphere and that a hydrogen atom migrates across the intact Ir-Ir metal bond. These results are consistent with the emerging trend that two-electron mixed-valence cores manage the two-electron chemistry of substrates with facility when hydrogen is the atom that migrates between metal centers.

  DOI：

  10.1021/ic049246l