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邻异丙硫基苯甲酰基和苯硫甲基铁衍生物的合成与反应
引用本文:赵达维,徐越,孙宝川,王志宏,唐良富.邻异丙硫基苯甲酰基和苯硫甲基铁衍生物的合成与反应[J].无机化学学报,2017,33(9):1547-1554.
作者姓名:赵达维  徐越  孙宝川  王志宏  唐良富
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, 天津 300071,南开大学化学学院, 元素有机化学国家重点实验室, 天津 300071,南开大学化学学院, 元素有机化学国家重点实验室, 天津 300071,南开大学化学学院, 元素有机化学国家重点实验室, 天津 300071,南开大学化学学院, 元素有机化学国家重点实验室, 天津 300071
基金项目:国家自然科学基金(No.21372124)和天津市自然科学基金(No.14JCYBJC19700)资助项目。
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)C6H4COFe(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C6H5SCH2Fe(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)C6H4COFe(CO)2I]2与2-吡啶硫醇钠(PySNa)反应得到单核配合物(o-iPrS)C6H4COFe(CO)2(SPy),但单核配合物C6H5SCH2Fe(CO)3I与PySNa反应导致其分解。另一方面,单核配合物C6H5SCH2Fe(CO)3I与三苯基膦(PPh3)反应得到羰基取代配合物C6H5SCH2Fe(CO)2(PPh3)I,但是双核配合物(o-iPrS)C6H4COFe(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。

关 键 词:硫醚  羰基铁  金属酰基配合物  吡啶  膦配体
收稿时间:2017/6/22 0:00:00
修稿时间:2017/7/20 0:00:00

Synthesis and Reactivity of ortho-Isopropylthiobenzoyl and Phenylthiomethyl Iron Derivatives
ZHAO Da-Wei,XU Yue,SUN Bao-Chuan,WANG Zhi-Hong and TANG Liang-Fu.Synthesis and Reactivity of ortho-Isopropylthiobenzoyl and Phenylthiomethyl Iron Derivatives[J].Chinese Journal of Inorganic Chemistry,2017,33(9):1547-1554.
Authors:ZHAO Da-Wei  XU Yue  SUN Bao-Chuan  WANG Zhi-Hong and TANG Liang-Fu
Institution:State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China,State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China,State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China,State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China and State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
Abstract:Reaction of isopropylthiobenzene with n-BuLi, and subsequently with iron carbonyl and iodine gave a dimeric ortho-isopropylthiobenzoyl iron derivative(o-iPrS)C6H4COFe(CO)2I]2 through two iodide bridges, while similar reaction of thioanisole only yielded mononuclear phenylthiomethyl iron complex C6H5SCH2Fe(CO)3I. These two complexes show significantly different reactivities upon treatment with various nucleophiles. For example, reaction of(o-iPrS)C6H4COFe(CO)2I]2 with sodium 2-pyridinethiolate (PySNa) give mononuclear complex (o-iPrS)C6H4COFe(CO)2(SPy), while reaction of C6H5SCH2Fe(CO)3I with PySNa results in the decomposition of the starting material. On the other hand, reaction of C6H5SCH2Fe(CO)3I with PPh3 give complex C6H5SCH2Fe(CO)2(PPh3)I, but no characterizable product is obtained from the similar reaction of(o-iPrS)C6H4COFe(CO)2I]2. All these newly synthesized compounds have been characterized by physico-chemical and spectroscopic methods, and their structures were unambiguously determined by X-ray crystallography.
Keywords:thioether  iron carbonyl  metal-acyl complex  pyridine  phosphine ligand
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