Iron carbonyl complexes of N,C,S-pincer ligands with a pendant thioether arm: Synthesis, structures and reactivity
Iron carbonyl complexes of N,C,S-pincer ligands with a pendant thioether arm: Synthesis, structures and reactivity
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DOI：
10.1016/j.poly.2017.10.014
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发表时间：
2017-10
期刊：
影响因子：
2.6
通讯作者：
M. Hirotsu;Kiyokazu Santo;Yuichiro Tanaka;I. Kinoshita
中科院分区：
文献类型：
--
作者：
M. Hirotsu;Kiyokazu Santo;Yuichiro Tanaka;I. Kinoshita
以4-甲酰基二苯并噻吩和2-（甲硫基或苯硫基）苯胺为原料合成了N，C，S-钳形配体与[Fe（CO）5]反应，合成了硫醇桥联的二铁羰基配合物。在金属化过程中发生的前配体中的C-S键的裂解。配合物中的羰基配体被硫醚S原子可逆地取代，允许N，C，S-三齿和S，N，C，S-四齿配位模式之间的相互转换。在温和条件下，S，N，C，S-四齿配体的二铁羰基配合物与二甲基苯基膦和4-（二甲氨基）吡啶反应，分别得到单核配合物和硫醇根桥联的二聚配合物，同时保持了S，N，C，S-四齿配位模式。通过与二甲基苯基膦的反应，将二聚络合物转化为单核络合物。
Thiolate-bridged diiron carbonyl complexes of N,C,S-pincer ligands with a pendant thioether arm were synthesized by treatment of [Fe(CO)5] with Schiff bases, which were derived from 4-formyldibenzothiophene and 2-(methylthio or phenylthio)aniline. Cleavage of a C–S bond in the proligands occurred during metalation. A carbonyl ligand in the complex was reversibly replaced by the thioether S atom, allowing for interconversion between the N,C,S-tridentate and S,N,C,S-tetradentate coordination modes. The diiron carbonyl complex of the S,N,C,S-tetradentate ligand reacted with dimethylphenylphosphine and 4-(dimethylamino)pyridine under moderate conditions to afford a mononuclear complex and a thiolate-bridged dimeric complex, respectively, while maintaining the S,N,C,S-tetradentate coordination mode. The dimeric complex was converted to the mononuclear complex by the reaction with dimethylphenylphosphine.