The influence of a peripheral functional group of diiron hexacarbonyl complexes on their electrochemistry and electrocatalytic reduction of proton
The influence of a peripheral functional group of diiron hexacarbonyl complexes on their electrochemistry and electrocatalytic reduction of proton
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二铁六羰基配合物外围官能团对其电化学和质子电催化还原的影响
DOI：
10.1016/j.electacta.2017.07.072
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发表时间：
2017-09
影响因子：
6.6
通讯作者：
Liu Xiaoming
中科院分区：
文献类型：
--
作者：
Zhong Wei;Xiao Zhiyin;Qian Guifen;Liu Xiaoming
本文报道了三个以萘-1，8-双硫醇骨架为桥键的六羰基二铁配合物（2，3，4）。为了比较，还制备了络合物4的质子化形式（4 H+）。它们在萘环的2位上分别带有一个官能团，即− CH 2 OH（2）、−COOH（3）、− CH 2N（Et）2（4）和− CH 2NH+（Et）2（4 H+）。配合物2是通过NaBH 4直接还原其带有醛基（-CHO，1）的前体而衍生的，而配合物3和4是通过Fe 3（CO）1,2分别与配体L2和L3反应常规合成的，配体L2和L3衍生自配体L1，萘并[1，8-cd][1，2]二硫杂环戊烯-3-甲醛。对配合物进行了表征，并对配合物3和4进行了X射线单晶衍射分析。用循环伏安法研究了配合物的电化学性质。络合物3的羧酸对第二次还原反应有显著影响，这是由于络合物3中的酸基团参与了与还原物种的反应。红外光谱数据和配合物的第一还原电位表明，这些官能团对金属中心几乎没有电子影响。然而，可以携带质子的官能团（-COOH和-CH 2N +H（Et）2）可以通过PCET（质子耦合电子转移）机制缓解质子还原催化的动力学。这些质子载体还可以通过在催化过程中充当质子中继来提高催化效率，如由三种络合物的峰电流对酸浓度的线性图所示。
Three diiron hexacarbonyl complexes (2,3and4) with naphthalene-1,8-bis(thiolate) skeleton as their bridging linkages are reported. For comparison, the protonated form of complex4was also prepared (4H+). They bear respectively a functional group on the naphthalene ring at the position 2,i.e. −CH2OH (2), −COOH (3), −CH2N(Et)2(4) and −CH2NH+(Et)2(4H+). Complex2was derived from the direct reduction of its precursor bearing aldehyde group (−CHO,1) by NaBH4while complexes3and4were routinely synthesized by reacting Fe3(CO)12with ligandsL2andL3, respectively, which were derived from ligandL1, naphtho[1,8-cd][1,2]dithiole-3-carbaldehyde. These complexes were fully characterized and complexes3and4were analyzed using X-ray single crystal diffraction. Electrochemistry of these complexes was also investigated by cyclic voltammetry. The carboxylic acid of complex3shows significant influence on the second reduction due to the acid group involving reaction with the reduced species. Both infrared spectral data and the first reduction potentials of the complexes suggest that these functional groups exert hardly electronic influence on the metal center. However, the functional groups which can carry proton (−COOH and −CH2N+H(Et)2) can ease the kinetics of the catalysis of proton reductionviaprobably PCET (proton-coupled electron transfer) mechanism. These proton carriers can also improve catalytic efficiency by acting a proton relay during the catalysis as suggested by the linear plots of peak current against acid concentration for the three complexes.
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