Oxido-Bridged Di-, Tri-, and Tetra-Nuclear Iron Complexes Bearing Bis(trimethylsilyl)amide and Thiolate Ligands

A series of di-, tri-, and tetra-nuclear iron-oxido clusters with bis­(trimethylsilyl)­amide and thiolate ligands were synthesized from the reactions of Fe­{N­(SiMe3)2}2 (1) with 1 equiv of thiol HSR (R = C6H5 (Ph), 4-tBuC6H4, 2,6-Ph2C6H3 (Dpp), 2,4,6-iPr3C6H2 (Tip)) and subsequent treatment with O2. The trinuclear clusters [{(Me3Si)2N}­Fe]3(μ3-O)­{μ-S­(4-RC6H4)}3 (R = H (3a), tBu (3b)) were obtained from the reactions of 1 with HSPh or HS­(4-tBuC6H4) and O2, while we isolated a tetranuclear cluster [{(Me3Si)2N}2Fe2(μ-SDpp)]2(μ3-O)2 (4) as crystals from an analogous reaction with HSDpp. Treatment of a tertrahydrofuran (THF) solution of 1 with HSTip and O2 resulted in the formation of a dinuclear complex [{(Me3Si)2N}­(TipS)­(THF)­Fe]2(μ-O) (5). The molecular structures of these complexes have been determined by X-ray crystallographic analysis.

以Fe{N(SiMe3)2}2（化合物1）为起始原料，分别与1当量的硫醇HSR（R = C6H5（苯基，Ph）、4-tBuC6H4、2,6-Ph2C6H3（二苯基苯基，Dpp）、2,4,6-iPr3C6H2（三异丙基苯基，Tip））进行反应，随后通入氧气（O2），成功合成了一系列带有双(三甲基硅基)胺基（bis(trimethylsilyl)amide）配体与硫醇盐（thiolate）配体的双核、三核及四核铁氧簇合物。当化合物1分别与苯硫酚（HSPh）或对叔丁基苯硫酚（HS(4-tBuC6H4)）反应后通入氧气，可得到三核簇合物[{(Me3Si)2N}Fe]3(μ3-O){μ-S(4-RC6H4)}3（R = H（3a）、叔丁基（3b））。而当与2,6-二苯基苯硫酚（HSDpp）进行类似反应时，我们分离得到了四核簇合物[{(Me3Si)2N}2Fe2(μ-SDpp)]2(μ3-O)2（4）的单晶。将化合物1的四氢呋喃（tetrahydrofuran，THF）溶液与2,4,6-三异丙基苯硫酚（HSTip）混合后通入氧气，得到双核配合物[{(Me3Si)2N}(TipS)(THF)Fe]2(μ-O)（5）。上述所有配合物的分子结构均通过X射线晶体衍射分析（X-ray crystallographic analysis）得以确定。