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首页> 外文期刊>Chemistry: A European journal >Hydrophilic Quaternary Ammonium-Group-Containing [FeFe]-Hydrogenase Models: Synthesis, Structures, and Electrocatalytic Hydrogen Production
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Hydrophilic Quaternary Ammonium-Group-Containing [FeFe]-Hydrogenase Models: Synthesis, Structures, and Electrocatalytic Hydrogen Production

机译：亲水性季铵基[FeFe]-加氢酶模型：合成，结构和电催化制氢

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摘要

The first quaternary ammonium-group-containing [FeFe]-hydrogenase models [(mu-PDT)Fe-2(CO)(4){kappa(2)-(Ph2P)(2)N(CH2)(2)NMe(2)BzBr}] (2; PDT=propanedithiolate) and [(mu-PDT)Fe-2(CO)(4){m-(Ph2P)(2)N(CH2)(2)NMe(2)BzBr}] (4) have been prepared by the quaternization of their precursors [(mu-PDT)Fe-2(CO)(4){kappa(2)-(Ph2P)(2)N(CH2)(2)NMe2}] (1) and [(mu-PDT)Fe-2(CO)(4){mu-(Ph2P)(2)N(CH2)(2)NMe2}] (3) with benzyl bromide in high yields. Although new complexes 1-4 have been fully characterized by spectroscopic and X-ray crystallographic studies, the chelated complexes 1 and 2 converted into their bridged isomers 3 and 4 at higher temperatures, thus demonstrating that these bridged isomers are thermodynamically favorable. An electrochemical study on hydrophilic models 2 and 4 in MeCN and MeCN/H2O as solvents indicates that the reduction potentials are shifted to less-negative potentials as the water content increases. This outcome implies that both 2 and 4 are more easily reduced in the mixed MeCN/H2O solvent than in MeCN. In addition, hydrophilic models 2 and 4 act as electrocatalysts and achieve higher i(cat)/i(p) values and turnover numbers (TONs) in MeCN/H2O as a solvent than in MeCN for the production of hydrogen from the weak acid HOAc.
机译：第一个含季铵盐的[FeFe]氢化酶模型[（mu-PDT）Fe-2（CO）（4）{kappa（2）-（Ph2P）（2）N（CH2）（2）NMe（ 2）BzBr}]（2; PDT =丙二硫丙烷）和[[mu-PDT）Fe-2（CO）（4）{m-（Ph2P）（2）N（CH2）（2）NMe（2）BzBr} ]（4）是通过对其前体[（mu-PDT）Fe-2（CO）（4）{kappa（2）-（Ph2P）（2）N（CH2）（2）NMe2}进行季铵化制备的。 （1）和[（mu-PDT）Fe-2（CO）（4）{mu-（Ph2P）（2）N（CH2）（2）NMe2}]（3）和苄基溴的高收率。尽管通过光谱学和X射线晶体学研究已经充分表征了新的配合物1-4，但是螯合的配合物1和2在较高的温度下转化为它们的桥接异构体3和4，因此证明这些桥接异构体在热力学上是有利的。对在MeCN和MeCN / H2O中作为溶剂的亲水模型2和4的电化学研究表明，随着水含量的增加，还原电势会转变为负电势。该结果表明，与MeCN相比，在混合的MeCN / H2O溶剂中2和4都更容易还原。此外，亲水模型2和4充当电催化剂，并且在MeCN / H2O作为溶剂中，从弱酸HOAc产生氢的过程中，获得的i（cat）/ i（p）值和周转率（TON）高于MeCN。 。

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