在這份研究中我們嘗試去探討高價鐵在多硫配位環境下的化學，所以我們分別利用tris(thiolato)phosphine ([PS3”]H3)以及bis(thiolato)phosphine ([PS2”]H2)配位基與鐵二價及鐵三價起始物進行反應。我們合成並純化出包含iron(III)-azide、bis(ligand) iron(III) 、bis(ligand) iron(IV)等三種鐵硫化合物。這些化合物同時也利用許多儀器加以鑑定，例如核磁共振光譜、紫外光/可見光光譜、K-edge X-ray吸收光譜以及電噴灑游離與循環伏安法等。這些化合物也經由X-ray繞射鑑定出結構。化合物1 [FeIIIPS3”N3][PPh4](1) 是一個不常見的鐵三價與疊氮鍵結的例子。其中心鐵金屬以雙三角錐的結構分別和tris(thiolato)phosphine四芽配位基與疊氮離子鍵結。化合物2 [FeIII(PS2”)2][PPh4](2)和化合物3 [FeIV(PS2”)2](3) 分別是鐵三價bis(ligand) 與鐵四價bis(ligand) 的物質。此兩種化合物中心鐵金屬皆為六配位的八面體結構。此外，為了得到高價鐵氮化合物如FeV≣N 或FeIV=NH 等結構，我們利用化合物1 [FeIIIPS3”N3][PPh4](1) 在Rayonet光化學反應器下進行了光分解反應。

In our effort to explore the high valent iron chemistry a S-rich ligation environment, we utilized tris(thiolato)phosphine ligand and bis(thiolato)phosphine ligand, [PS3”]H3 and [PS2”]H2, respectively, to react with ion(II) and iron(III) strating materials. Three iron-thiolate complexes including one iron(III)-azide species, a bis(ligand) iron(III) complex and a bis(ligand) iron(IV) complex have been synthesized in a pure form. They have been also characterized by various techniques such as NMR, UV-Vis-NIR, and K-edge X-ray absorption spectroscopies, as well as ESI-MS and Cyclic Voltammetry. In addition, the structures were also analyzed by X-ray crystallography. First complex, [FeIIIPS3”N3][PPh4](1), is a rare example of an azide bound iron(III) species. The metal center adopts a trigonal bipyramidal geometry by binding to a tetradentate title ligand and an azide ion. The second complex, [FeIII(PS2”)2][PPh4](2), is a bis(ligand) of iron(III) complex and the third one, [FeIV(PS2”)2](3), is bis(ligand) of iron(IV) complex. The last two complexes both have six-coordinated octahedral iron centers. In order to generate high-valent iron nitride complexes such as FeV≣N or FeIV=NH, the photolysis of [FeIIIPS3”N3][PPh4](1) was carried out by using Rayonet Photochemical Reactor.

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