Synthesis and characterisation of three diiron tetracarbonyl complexes related to the diiron centre of [FeFe]-hydrogenase and their protonating, electrochemical investigations
Synthesis and characterisation of three diiron tetracarbonyl complexes related to the diiron centre of [FeFe]-hydrogenase and their protonating, electrochemical investigations
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与[FeFe]-氢化酶二铁中心相关的三种二铁四羰基配合物的合成和表征及其质子化、电化学研究
DOI：
10.1039/b903758f
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发表时间：
2009-07
影响因子：
3.3
通讯作者：
中科院分区：
文献类型：
--
作者：
三个四羰基二铁配合物[Fe_2（SCH_2）_2C（Me）（CH_2 OR）（PNP）（CO）_4]的合成与表征（R = H且PNP = L11：2; R = H且PNP = L22：3; R = Ts且PNP = L11：4）作为[FeFe]-氢化酶的二铁亚基的模型，其中OTs、L11和L22分别是甲苯磺酸盐、（Ph 2 P）2NCH 2（2-C5 H4 N）和（Ph 2 P）2NCH 2 Ph，分别这些配合物的充分特点和晶体学确定的复杂4的结构。用红外光谱和核磁共振谱研究了这些配合物与HBF_4·Et_2O的质子化反应，发现在加入酸后不能形成氢化物。相反，添加过量的酸导致PNP骨架的N原子质子化，如晶体学分析所揭示的，由于参与与Fe-Fe中心的共辄相互作用，PNP骨架是弱碱。研究了这些配合物的电化学性质及其对质子的电催化还原。我们的研究结果表明，吡啶侧基的存在可以降低质子还原的过电位，但在我们的情况下，似乎并没有提高电催化效率。
The synthesis, characterisation of three diiron tetracarbonyl complexes, [Fe2(SCH2)2C(Me)(CH2OR)(PNP)(CO)4] (R = H and PNP = L11: 2; R = H and PNP = L22: 3; R = Ts and PNP = L11: 4) as models for the diiron sub-unit of [FeFe]-hydrogenase are described, where OTs, L11 and L22 are toluenesulfonate, (Ph2P)2NCH2(2-C5H4N) and (Ph2P)2NCH2Ph, respectively. These complexes are fully characterised and the structure of complex 4 is crystallographically determined. Protonation of these complexes with HBF4·Et2O is probed by using infrared and NMR spectroscopies which reveals that no hydride can be formed upon addition of the acid. Instead addition of excess of the acid leads to protonating the N atom of the PNP skeleton, which is a weak base due to participating conjugating interactions with the Fe–Fe centre, as revealed by crystallographic analysis. Electrochemistry of these complexes and their electrocatalytic reduction of protons are also investigated. Our results suggest that the existence of the pendant pyridine group can lower the overpotential for proton reduction but does not seem to enhance electrocatalytic efficiency in our case.
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影响因子：
4.6
作者：
T. Rauchfuss
通讯作者：
T. Rauchfuss
影响因子：
6.8
作者：
J. Peters
通讯作者：
J. Peters
影响因子：
3.8
作者：
Shi Jiang;Jianhui Liu;Licheng Sun
通讯作者：
Shi Jiang;Jianhui Liu;Licheng Sun
影响因子：
4.6
作者：
Ezzaher, Salah;Capon, Jean-Francois;Talarmin, Jean
通讯作者：
Talarmin, Jean
影响因子：
4
作者：
Adam, Fatima I.;Hogarth, Graeme;Sanchez, Benjamin E.
通讯作者：
Sanchez, Benjamin E.