(η1-dioxygen)(1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine)copper(I) trifluoromethanesulfonate | 960157-64-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (η1-dioxygen)(1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine)copper(I) trifluoromethanesulfonate
• CAS: 960157-64-6
• 化学式: CF₃O₃S*C₂₁H₄₈CuN₁₀O₂
• 分子量: 685.294
• InChiKey: OUYPLQDVEXSVAH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  (η1-dioxygen)(1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine)copper(I) trifluoromethanesulfonate 以 N,N-二甲基甲酰胺-d7 为溶剂， 生成 (1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine)copper(I) trifluoromethanesulfonate
  参考文献：
  名称：

  Isotopic Probing of Molecular Oxygen Activation at Copper(I) Sites

  摘要：

  Copper-dioxygen (CUO2) adducts are frequently proposed as intermediates in enzymes, yet their electronic and vibrational structures have not always been understood. [Cu(eta(1)-O-2)TMG(3)tren](+) (TMG(3)-tren = 1,1,1-tris{2-[N-2-(1,1,3,3-tetramethylguanidino)]ethyl}amine) features end-on (eta(1)) O-2 coordination in the solid state. Described here is an investigation of the compound's solution properties by nuclear magnetic resonance spectroscopy, density functional calculations, and oxygen isotope effects. The study yields two major findings. First, [CU(eta(1)-O-2)TMG(3)tren](+) is paramagnetic due to a triplet electronic structure; this is in contrast to other copper compounds where O-2 is bound in a side-on manner. Second, the oxygen equilibrium isotope effect upon O-2 binding to copper(I) (O-18 EIE equivalent to K((OO)-O-16-O-16)IK((OO)-O-16-O-18) = 1.0148 +/- 0.0012) is significantly larger than those determined for iron and cobalt eta(1)-O-2 adducts. This result is suggested to reflect greater ionic (Cu-II-O-2(-1)) character within the valence bond description. A revised interpretation of the physical origins of the O-18 ElEs upon O-2 binding to redox metals is also advanced along with experimental data that should be used as benchmarks for interpreting O-18 kinetic isotope effects upon enzyme reactions.

  DOI：

  10.1021/ja074620c
• 作为产物：
  描述：

  (1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine)copper(I) trifluoromethanesulfonate 、 氧气 以 N,N-二甲基甲酰胺-d7 为溶剂， 生成 (η1-dioxygen)(1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine)copper(I) trifluoromethanesulfonate
  参考文献：
  名称：

  Isotopic Probing of Molecular Oxygen Activation at Copper(I) Sites

  摘要：

  Copper-dioxygen (CUO2) adducts are frequently proposed as intermediates in enzymes, yet their electronic and vibrational structures have not always been understood. [Cu(eta(1)-O-2)TMG(3)tren](+) (TMG(3)-tren = 1,1,1-tris{2-[N-2-(1,1,3,3-tetramethylguanidino)]ethyl}amine) features end-on (eta(1)) O-2 coordination in the solid state. Described here is an investigation of the compound's solution properties by nuclear magnetic resonance spectroscopy, density functional calculations, and oxygen isotope effects. The study yields two major findings. First, [CU(eta(1)-O-2)TMG(3)tren](+) is paramagnetic due to a triplet electronic structure; this is in contrast to other copper compounds where O-2 is bound in a side-on manner. Second, the oxygen equilibrium isotope effect upon O-2 binding to copper(I) (O-18 EIE equivalent to K((OO)-O-16-O-16)IK((OO)-O-16-O-18) = 1.0148 +/- 0.0012) is significantly larger than those determined for iron and cobalt eta(1)-O-2 adducts. This result is suggested to reflect greater ionic (Cu-II-O-2(-1)) character within the valence bond description. A revised interpretation of the physical origins of the O-18 ElEs upon O-2 binding to redox metals is also advanced along with experimental data that should be used as benchmarks for interpreting O-18 kinetic isotope effects upon enzyme reactions.

  DOI：

  10.1021/ja074620c