Photoinduced Terminal Hydride of [FeFe]-Hydrogenase Biomimetic Complexes
Photoinduced Terminal Hydride of [FeFe]-Hydrogenase Biomimetic Complexes
复制标题
[FeFe]-氢化酶仿生复合物的光诱导末端氢化物
DOI：
10.1021/acs.inorgchem.9b01738
复制
发表时间：
2019
影响因子：
4.6
通讯作者：
Hall, Michael B.
中科院分区：
文献类型：
--
作者：
Niu, Shuqiang;Nelson, Anne E.;De La Torre, Patricia;Li, Haixia;Works, Carmen F.;Hall, Michael B.
[FeFe]-氢化酶（[FeFe]-H2 ase）的活性位点在关键的H簇中间体Hhyd中具有桥接羰基配体和末端氢化物。然而，到目前为止，几乎所有报道的合成模拟物都更喜欢用氢化物桥接两个铁，只有少数具有末端氢化物的模拟物是通过调节庞大的二膦配体的空间效应获得的。此外，尽管在[FeFe]-H2酶模拟物[Fe 2（μ-pdt）（μ-H）（CO）4（PMe 3）2]+（1H+）中，在质子化过程或氢交换过程中存在具有末端氢化物或质子化桥接硫醇盐配体的中间体，但通过时间分辨IR光谱仅观察到桥接硫醇盐。在本报告中，1H+的FTIR光谱，在CO和较长的照射时间，揭示了几个新的光诱导物种。除了CO损失物种，许多光诱导的产品可以分配到1H+与终端氢化物通过比较它们的CO振动频率与密度泛函理论计算。
The active site of the [FeFe]-hydrogenase ([FeFe]-H2ase) has a bridging carbonyl ligand and a terminal hydride in the key H-cluster intermediate Hhyd. However, nearly all of the synthetic mimics reported, so far, prefer a hydride bridging the two irons, and only few mimics with a terminal hydride were achieved by tuning the steric effects of bulky diphosphine ligands. Moreover, although intermediates with either a terminal hydride or a protonated bridging thiolate ligand were proposed to exist during protonation processes or hydrogen exchange in the [FeFe]-H2ase mimic, [Fe2(μ-pdt)(μ-H)(CO)4(PMe3)2]+(1H+), only bridging hydrides were observed by time-resolved IR spectroscopy. In this report, FTIR spectroscopy of1H+, under CO with longer irradiation time, revealed several new photoinduced species. In addition to the CO loss species, many of the photoinduced products can be assigned to1H+with a terminal hydride by comparison of their CO vibrational frequencies with density functional theory calculations.