本文選題：雙核鐵硫簇化合物 + 1��； 參考：《大連理工大學》2014年碩士論文

【摘要】：鐵硫簇化合物在自然界中廣泛存在,它在生物體酶物質(zhì)中充當活性中心結(jié)構(gòu)單元,由于酶溫和、高效的催化能力,引起了化學工作者對其核心結(jié)構(gòu)——簇類化合物的結(jié)構(gòu)和功能的濃厚興趣。我們課題組致力于雙核鐵硫簇仿生固氮酶模型的研究和設計,通過對硫配體的結(jié)構(gòu)修飾我們發(fā)現(xiàn)不同的硫配體對鐵硫簇化合物的性質(zhì)具有很大的影響。1,8-萘酰亞胺類化合物不僅具有優(yōu)良的熒光發(fā)射功能,而且具有很好的電子傳遞和誘導功能,同時此類化合物結(jié)構(gòu)易于修飾。本文以1,8-萘酰亞胺類化合物為配體,成功合成了7個新型鐵硫簇配合物,具體內(nèi)容如下： (1)以苊為原料通過鹵代、氧化、酰胺化、硫代等步驟合成了配體1,N-正丁基-4,5-二硫萘酰亞胺； (2) Fe(CO)5分別與Cp*,cp'和Cp反應得到了配合物2a:[Fe(CO)2Cp*]2,2b:[Fe(CO)2Cp']2和2c:[Fe(CO)2Cp]2(Cp*=η5-C5Me52a；Cp'=η6-C5Me42b；Cp=η5-C5H53c), (3)合成了2個茂基側(cè)面配位,CO橋聯(lián)配位的1,8-萘酰亞胺類雙核鐵硫簇化合物[cpFe(μ2-4,5-S2-R)(μ-CO)FeCp*](3a:Cp=η5-C5Me5,3b:Cp=η5-C5Me4,R=N-正丁基-1,8-萘酰亞胺),用HBF4(乙醚溶液)對3a進行氧化得到了化合物3a[BF4]并且測定了配合物3a、3b的電化學循環(huán)曲線；以配體1與配體3c反應,得到了脫硫的雙核鐵配合物4:[μ5-C5H5)2Fe2(C16N1O2S1)2]； (4)以3a[BF4]與NO反應得到了茂基側(cè)面配位、NO橋聯(lián),以1,8-萘酰亞胺為配體的雙核鐵硫簇化合物5:[Cp*Fe(μ2-4,5-S2-R)(,μ-NO)FeCp*][BF4]； (5)以3a[BF4]與三乙基芐基氯化銨(TEBAC)反應,合成了茂基側(cè)配位、三羰基端配位的1,8-萘酰亞胺類雙核鐵硫簇化合物6:[Cp*Fe(CO)2(μ2-4,5-S2-R)(CO)FeCp*]。 以上產(chǎn)物通過1H NMR、IR、質(zhì)譜、X-ray單晶衍射等分析表征手段確定了其結(jié)構(gòu)。
[Abstract]:Iron-sulfur cluster compounds are widely found in nature. They act as active central structural units in enzymes, due to their mild and efficient catalytic ability. It has aroused great interest in the structure and function of its core structure-cluster compounds. Our research group is devoted to the research and design of bionic nitrogenase model of binuclear iron-sulfur clusters. Through the structural modification of sulfur ligands, we found that different sulfur ligands have great influence on the properties of iron sulfur cluster compounds. It also has good electron transfer and inductive function, and the structure of this kind of compound is easy to modify. In this paper, seven new iron-sulfur cluster complexes have been successfully synthesized by using 1 ~ (8) -naphthalimide as ligands. The main contents are as follows: (1) Ligand 1, N-butyl -4- (5-dithionaphthalimide) was synthesized from acenaphthene by halogenation, oxidation, amidation and thioylation. (2) the complexes 2a: [FeCOCOO2Cp*] 2Cp*: [FecoCO2Cp'] 2 and 2c: [Fe(CO)2Cp] 2CpPU = 畏 5-C5Me52aCpN = 畏 6-C5Me42bCp = 畏 5-C5C5H53cPN were obtained by the reaction of Fe(CO)5 with CpP' and CP, respectively. Two binuclear iron-sulfur clusters of 1,4-naphthalimide [cpFe (渭 2-4N, 5-S 2-S 2-RN) (渭 -CO-C5 FeCp*] 3a: CP = 畏 5-C5Me5M5N 3bwt Cp= 畏 5-C5Me4N = N-n-butyl-1-butadiene-8-naphthalimide) were synthesized. The compounds 3a [BF4] were oxidized by HBF4 (ether solution) to 3a [BF4]. The electrochemical cycle curve of 3a ~ 3b; The binuclear iron complex 4: [渭 5-C5H5)2Fe2(C16N1O2S1)2] was obtained by the reaction of ligand 1 with ligand 3c. In the reaction of 3 a [BF4] with no, no bridging was obtained. The binuclear iron-sulfur cluster compound 5: [CpnFe5 (渭 2-4C5-S2-RHN, 渭 -NO-FeCp*] [BF4]; " In the reaction of 3a [BF4] with triethylbenzylammonium chloride (TEBAC), a trichlorocarbonyl ligand, a trichloro 8-naphthalimide binuclear iron-sulfur cluster compound 6, was synthesized. [CpFE-FeCO2 (渭 2-4N 5-S2-RCOFeCp*]) was synthesized and characterized by the chemical reaction of triethylbenzylammonium chloride and triethylbenzylammonium chloride (triethylbenzylammonium chloride). The above products were characterized by 1H NMRIR, mass spectrometry and X-ray single crystal diffraction.
【學位授予單位】：大連理工大學
【學位級別】：碩士
【學位授予年份】：2014
【分類號】：R914.5

【共引文獻】

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8 O淳，

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