Internal Reorganization Energies for Copper Redox Couples: The Slow Electron-Transfer Reactions of the [CuII/I(bib)2]2+/+ Couple
Internal Reorganization Energies for Copper Redox Couples: The Slow Electron-Transfer Reactions of the [CuII/I(bib)2]2+/+ Couple
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铜氧化还原对的内部重组能：[CuII/I(bib)2]2/对的慢电子转移反应
DOI：
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发表时间：
1999
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通讯作者：
D. Stanbury
中科院分区：
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作者：
Boping Xie;T. Elder;§. A. Lon J. Wilson;D. Stanbury
[CuII(bib)2]2+ 和 [CuI(bib)2]+ (bib = 2,2'-双(2-咪唑基)联苯) 具有相似的几何形状，其中 Cu(II) 配合物最好描述为伪方形平面，而 Cu(I) 配合物则为伪四面体。乙腈中的循环伏安图只是准可逆的，ΔEp/p ∼ 103 mV，这导致 E1/2 的不确定性。反应的 UV−vis 测量 [CuII(bib)2]2+ + [CoII((nox)3(BC6H5)2)] ⇌ [CuI(bib)2]+ + [CoIII((nox)3(BC6H5)2)]+ ((nox)3(BC6H5)2 = 笼形螯合物配体) 产量 K = 2.6，在乙腈中，25 °C，μ = 0.1 M (Et4NBF4)。使用 CoIII/II 电对的已知 E°，可得出 [CuII/I(bib)2]2+/+ 的 E° = 0.274 V vs Ag/AgCl。这反过来导致与 [CoII((nox)3(BC4H9)2)] 反应的 K = 72。 [CuII(bib)2]2+ 与 [CoII((nox)3(BC4H9)2)] 的反应遵循简单的双分子动力学，k = 87 M-1 s-1。使用 [CoII((nox)3(BC6H5)2)] 和 [CoII((dmg)3(BC4H9)2)] 作为还原剂时会发生类似的行为。 k11 = 0.16 M-1 s-1 的值是针对 [CuII(bib)2]2+/[CuI(bib)2]+ 自交换计算得出的...
[CuII(bib)2]2+ and [CuI(bib)2]+ (bib = 2,2‘-bis(2-imidazolyl)biphenyl) have similar geometries, with the Cu(II) complex best described as pseudo-square planar and the Cu(I) complex pseudo-tetrahedral. The cyclic voltammograms in acetonitrile are only quasi-reversible, with ΔEp/p ∼ 103 mV, which leads to uncertainty in E1/2. UV−vis measurements of the reaction [CuII(bib)2]2+ + [CoII((nox)3(BC6H5)2)] ⇌ [CuI(bib)2]+ + [CoIII((nox)3(BC6H5)2)]+ ((nox)3(BC6H5)2 = a clathrochelate ligand) yield K = 2.6 in acetonitrile at 25 °C with μ = 0.1 M (Et4NBF4). Using the known E° for the CoIII/II couple yields E° = 0.274 V vs Ag/AgCl for [CuII/I(bib)2]2+/+. This, in turn, leads to K = 72 for reaction with [CoII((nox)3(BC4H9)2)]. The reaction of [CuII(bib)2]2+ with [CoII((nox)3(BC4H9)2)] obeys simple bimolecular kinetics with k = 87 M-1 s-1. Similar behavior occurs with [CoII((nox)3(BC6H5)2)] and [CoII((dmg)3(BC4H9)2)] as reductants. A value of k11 = 0.16 M-1 s-1 is calculated for the [CuII(bib)2]2+/[CuI(bib)2]+ self-exch...