Synthesis, structure, and ligand-based reduction reactivity of trivalent organosamarium benzene chalcogenolate complexes (C5Me5)2Sm(EPh)(THF) and [(C5Me5)2Sm(μ-EPh)]2
Synthesis, structure, and ligand-based reduction reactivity of trivalent organosamarium benzene chalcogenolate complexes (C5Me5)2Sm(EPh)(THF) and [(C5Me5)2Sm(μ-EPh)]2
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DOI：
10.1021/ic0502170
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发表时间：
2005-06-13
影响因子：
4.6
通讯作者：
Ziller, JW
中科院分区：
文献类型：
--
作者：
Evans, WJ;Miller, KA;Ziller, JW
合成了(C5Me5)(3)Sm(E=S，Se，Te)配合物，并用(C5Me5)(3)Sm还原的底物(C5Me5)(3)Sm：环辛四烯、偶氮苯、吩嗪处理(C5Me5)(3)Sm：环辛四烯、偶氮苯、吩嗪，比较了茂金属环境下(Eph)(-)配体与(C5Me5)(3)Sm的空间诱导还原化学。PhEEPh分别与(C5Me5)(2)Sm(THF)(2)和(C5Me5)(2)Sm(THF)反应生成了四氢呋喃溶剂化的单金属配合物(C5Me5)(2)Sm(Ph)(THF)和它们的非溶剂化二聚体类似物[(C5Me5)(2)Sm(Mu-Eph)](2)。两组顺磁性苯硫醇配合物均经X-单晶学确证，并形成同源系列。只有(TePh)(-)络合物表现出还原反应活性，并且只有在加热到65℃时才表现出还原反应活性。
To compare the ligand-based reduction chemistry of (EPh)(-) ligands in a metallocene environment to the sterically induced reduction chemistry of the (C5Me5)(-) ligands in (C5Me5)(3)SM, (C5Me5)(2)Sm(EPh) (E = S, Se, Te) complexes were synthesized and treated with substrates reduced by (C5Me5)(3)SM: cyclooctatetraene; azobenzene; phenazine. Reactions of PhEEPh with (C5Me5)(2)Sm(THF)(2) and (C5Me5)(2)SM produced THF-solvated monometallic complexes, (C5Me5)(2)SM(Ph)(THF), and their unsolvated dimeric analogues, [(C5Me5)(2)Sm(mu-EPh)](2), respectively. Both sets of the paramagnetic benzene chalcogenolate complexes were definitively identified by X-crystallography and form homologous series. Only the (TePh)(-) complexes show reduction reactivity and only upon heating to 65 degrees C.