Pyridyl- and pyrimidyl-phosphine-substituted [FeFe]-hydrogenase mimics: Synthesis, charaterization and properties
Pyridyl- and pyrimidyl-phosphine-substituted [FeFe]-hydrogenase mimics: Synthesis, charaterization and properties
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吡啶基和嘧啶基膦取代的 [FeFe]-氢化酶模拟物：合成、表征和性质
DOI：
10.1016/j.jorganchem.2014.04.026
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发表时间：
2014-09-15
影响因子：
2.3
通讯作者：
Chen, Chang-Neng
中科院分区：
文献类型：
--
作者：
Cui, Hong-Hua;Wu, Nan-Nan;Chen, Chang-Neng
两个四核铁硫络合物{[(mu-pdt)Fe-2(CO)(5)](2)(PNP) (2)和[(mu-pdt)Fe-2(CO)(5)](2)(PNNP) (3)}和三个双核铁硫络合物{[(mu-pdt)Fe-2(CO)(5)](PNP) (4)，使用两种新的嘧啶基膦配体 PNNP [4,6-双（二苯基膦）嘧啶]和 PNN（4-叔丁基-6-二苯基膦嘧啶）以及报道的材料合成了 [(mu-pdt)Fe-2(CO)(5)](PNNP) (5) 和 [(mu-pdt) Fe-2(CO)(5)](PNN) (6)}吡啶基膦 PNP [双(二苯基膦)吡啶]作为取代基与 Fe-2(mu-pdt)(CO)(6) 反应。通过单晶X射线分析证实了2、3和6的分子结构，表明所有膦配体均占据顶端位置，而3（P21/n）的空间群与2（P-1）不同。循环伏安图显示，嘧啶基膦取代的配合物3、5和6在CH2Cl2溶液中呈现出两个还原波，而吡啶基膦取代的配合物2和4仅呈现出一个还原波。 DFT 计算研究表明，两个 Fe2S2 中心和连接的 PNNP 配体对 3 的 LUMO 的贡献相当，这与本工作中其他 [Fe2S2] 模拟物的贡献不同。 (C) 2014 Elsevier B.V. 保留所有权利。
Two tetranuclear iron-sulphur complexes {[(mu-pdt)Fe-2(CO)(5)](2)(PNP) (2) and [(mu-pdt)Fe-2(CO)(5)](2)(PNNP) (3)} and three dinuclear ones {[(mu-pdt)Fe-2(CO)(5)](PNP) (4), [(mu-pdt)Fe-2(CO)(5)](PNNP) (5) and [(mu-pdt) Fe-2(CO)(5)](PNN) (6)} were synthesized, using two new pyrimidyl-phosphine ligands PNNP [4,6-bis( diphenylphosphino) pyrimidine] and PNN (4-tertiary butyl-6-diphenylphosphino pyrimidine) together with the reported pyridyl-phosphine PNP [bis(diphenylphosphino) pyridine] as substituents to react with Fe-2(mu-pdt)(CO)(6). The molecular structures of 2, 3 and 6 were confirmed by single-crystal X-ray analyses, which show that all phosphine ligands occupy the apical positions, while the space group of 3 (P21/n) is different from that of 2 (P-1). Cyclic voltammograms reveal that pyrimidyl-phosphine substituted complexes 3, 5 and 6 present two reduction waves in CH2Cl2 solutions, while pyridylphosphine substituted 2 and 4 show only one. The DFT computational studies demonstrate that the contributions to the LUMO of 3 are comparable from the two Fe2S2 centres and ligated PNNP ligand, which is different from those of other [Fe2S2] mimics in this work. (C) 2014 Elsevier B. V. All rights reserved.