邻异丙硫基苯甲酰基和苯硫甲基铁衍生物的合成与反应（英文）

发布时间：2019-04-19 21:24

【摘要】：利用异丙基苯硫醚与丁基锂反应后,再依次与羰基铁和碘反应制得了碘桥双核邻异丙硫基苯甲酰基铁配合物[(o-~iPrS)C_6H_4COFe(CO)_2I]2,而苯甲硫醚类似的反应却仅得到单核苯硫甲基铁配合物C_6H_5SCH_2Fe(CO)_3I。当与亲核试剂作用时,这2个化合物表现出显著不同的反应活性。如双核配合物[(o-~iPrS)C_6H_4COFe(CO)_2I]2与2-吡啶硫醇钠(Py SNa)反应得到单核配合物(o-~iPrS)C_6H_4COFe(CO)_2(SPy),但单核配合物C_6H_5SCH_2Fe(CO)_3I与Py SNa反应导致其分解。另一方面,单核配合物C_6H_5SCH_2Fe(CO)_3I与三苯基膦(PPh3)反应得到羰基取代配合物C_6H_5SCH_2Fe(CO)_2(PPh3)I,但是双核配合物[(o-~iPrS)C_6H_4COFe(CO)_2I]2类似的反应却导致其分解,没有获得可表征的化合物。所有新合成的化合物都通过了核磁与红外光谱的表征,它们的结构也获得了X射线单晶衍射的确证。
[Abstract]:[(o-~iPrS) C_6H_4COFe (CO) _ 2i] _ 2 was synthesized by the reaction of isopropyl phenylthioether with lithium butyllithium and then with iron carbonyl and iodine in turn to give iodobridge binuclear o-isopropylthiobenzoyl iron complex [(iodobridge) C_6H_4COFe (CO) _ 2i] _ 2, However, the similar reaction of anisosulfide gave only the monuclear phenylene thiomethyl iron complex C_6H_5SCH_2Fe (CO) _ 3I. When reacted with nucleophilic reagent, the two compounds showed significantly different reactivity. For example, binuclear complex [(o-~iPrS) C_6H_4COFe (CO) _ 2i] _ 2 reacts with 2-pyridinthiol sodium (Py SNa) to give (o-~iPrS) C_6H_4COFe (CO) _ 2 (SPy),. However, the reaction of monuclear complex C_6H_5SCH_2Fe (CO) _ 3i with Py SNa resulted in its decomposition. On the other hand, the monuclear complex C_6H_5SCH_2Fe (CO) _ 3i reacts with triphenylphosphine (PPh3) to give the carbonyl substituted complex C_6H_5SCH_2Fe (CO) _ 2 (PPh3) I. However, a similar reaction of the binuclear complex [(o-~iPrS) C_6H_4COFe (CO) _ 2i] _ 2 led to the decomposition of the binuclear complex [(C_6H_4COFe (CO) _ 2i)] _ 2, and no characterizable compounds were obtained. All the newly synthesized compounds were characterized by NMR and IR spectra, and their structures were confirmed by X-ray single crystal diffraction.
【作者单位】：南开大学化学学院元素有机化学国家重点实验室;
【基金】：国家自然科学基金(No.21372124) 天津市自然科学基金(No.14JCYBJC19700)资助项目
【分类号】：O641.4

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