The electrochemical ion-transfer reactivity of porphyrinato metal complexes in 4-(3-phenylpropyl)pyridine | water systems
The electrochemical ion-transfer reactivity of porphyrinato metal complexes in 4-(3-phenylpropyl)pyridine | water systems
复制标题
卟啉金属配合物在4-(3-苯基丙基)吡啶中的电化学离子转移反应活性
DOI：
10.1039/b514348a
复制
发表时间：
2006
影响因子：
3.3
通讯作者：
F. Marken
中科院分区：
文献类型：
--
作者：
M. Bonné;C. Reynolds;Stuart Yates;G. Shul;Joanna Niedziółka;M. Opallo;F. Marken
离子在水相和有机相之间的转移是在石墨|4-(3-苯丙基)吡啶|水电解液的三相交界处通过电化学驱动的。四苯基卟啉(TPP)金属络合物(MnTPP+、FeTPP+、CoTPP)和氯化血红素易溶于4-(3-苯丙基)吡啶有机相中，并经历氧化/还原过程，这些过程与液/液离子转移相耦合。为了保持电荷中性，每个单电子氧化(还原)过程都与一个阴离子(这里是PF6−、ClO4−、SCN−、NO3−、OCN−或CN−)从水(有机)转移到有机(水)相耦合。所研究的阴离子范围允许研究疏水性和络合物形成(阴离子与金属中心的缔合)的影响。开发了一个初步的动力学方案来量化络合物的形成、促进阴离子转移和竞争阳离子转移过程。探讨了有机溶剂对离子转移过程的影响。对于可逆的氰化物转移过程，观察到了非常强的结合和特殊的效应。
The transfer of ions between an aqueous and an organic phase is driven electrochemically at a triple phase junction graphite | 4-(3-phenylpropyl)pyridine | aqueous electrolyte. Tetraphenylporphyrinato (TPP) metal complexes (MnTPP+, FeTPP+, CoTPP) and hemin readily dissolve in the organic 4-(3-phenylpropyl)pyridine phase and undergo oxidation/reduction processes which are coupled to liquid | liquid ion transfer. In order to maintain charge neutrality, each one-electron oxidation (reduction) process is coupled to the transfer of one anion (here PF6−, ClO4−, SCN−, NO3−, OCN−, or CN−) from the aqueous (organic) into the organic (aqueous) phase. The range of anions studied allows effects of hydrophobicity and complex formation (association of the anion to the metal center) to be explored. A preliminary kinetic scheme is developed to quantify complex formation, facilitated anion transfer, and competing cation transfer processes. The effects of the organic solvent on the ion transfer processes are explored. Very strong binding and specific effects are observed for the reversible cyanide transfer process.