Abstract

As the biomimetic models of [FeFe]-hydrogenase active sites, two new di- and mononuclear iron complexes with chelating PNP ligands (PNP = (Ph₂P)₂NR) have been prepared and structurally determined by single-crystal X-ray diffraction analysis. Treatment of precursor Fe₂(μ-edt)(CO)₆ (A, edt = SCH₂CH₂S) with diphosphine (Ph₂P)₂N(CHMe₂) in the presence of Me₃NO·2H₂O in MeCN produced a dinuclear iron complex Fe(μ-edt)(CO)₄{κ²-(Ph₂P)₂N(CHMe₂)} (1), whereas the similar reaction of Fe₂(μ-odt)(CO)₆ (B, odt = SCH₂OCH₂S) with (Ph₂P)₂N(CH₂)₃Me afforded a mononuclear iron complex Fe(κ²-odt)(CO)₂{κ²-(Ph₂P)₂N(CH₂)₃Me} (2). The crystal structure of 1 contains a butterfly [Fe₂S₂] cluster, whereas that of 2 exhibits a square bipyramidal geometry of Fe atom.

摘要

作为[FeFe]-加氢酶活性位点的仿生模型，已制备了两种具有螯合PNP配体（PNP =（Ph ₂ P）₂ NR）的新型二核和单核铁配合物，并通过单晶X射线衍射确定了结构分析。在Me ₃ NO·2H ₂ O存在下，用二膦（Ph ₂ P）₂ N（CHMe ₂）处理前体Fe ₂（μ- edt）（CO）₆（A，edt = SCH ₂ CH ₂ S）。的MeCN产生的双核铁络合物的Fe（μ -edt）（CO）₄ { κ ²-（Ph ₂ P）₂ N（CHMe ₂）}（1），而Fe ₂（μ- odt）（CO）₆（B，odt = SCH ₂ OCH ₂ S）与（Ph ₂ P）的相似反应₂ N（CH ₂）₃我得到的单核铁络合物的Fe（κ ² -odt）（CO）₂ { κ ² - （PH ₂ P）₂ N（CH ₂）₃我}（2）。1的晶体结构含有蝴蝶的[Fe ₂小号₂ ]簇，而那的2件展品的Fe原子的平方双锥。