含1,8-萘酰亚胺铁硫簇的合成、结构与性能研究

发布时间：2018-05-20 14:54

本文选题：双核铁硫簇化合物 + 1　；参考：《大连理工大学》2014年硕士论文

【摘要】：铁硫簇化合物在自然界中广泛存在,它在生物体酶物质中充当活性中心结构单元,由于酶温和、高效的催化能力,引起了化学工作者对其核心结构——簇类化合物的结构和功能的浓厚兴趣。我们课题组致力于双核铁硫簇仿生固氮酶模型的研究和设计,通过对硫配体的结构修饰我们发现不同的硫配体对铁硫簇化合物的性质具有很大的影响。1,8-萘酰亚胺类化合物不仅具有优良的荧光发射功能,而且具有很好的电子传递和诱导功能,同时此类化合物结构易于修饰。本文以1,8-萘酰亚胺类化合物为配体,成功合成了7个新型铁硫簇配合物,具体内容如下： (1)以苊为原料通过卤代、氧化、酰胺化、硫代等步骤合成了配体1,N-正丁基-4,5-二硫萘酰亚胺； (2) Fe(CO)5分别与Cp*,cp'和Cp反应得到了配合物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个茂基侧面配位,CO桥联配位的1,8-萘酰亚胺类双核铁硫簇化合物[cpFe(μ2-4,5-S2-R)(μ-CO)FeCp*](3a:Cp=η5-C5Me5,3b:Cp=η5-C5Me4,R=N-正丁基-1,8-萘酰亚胺),用HBF4(乙醚溶液)对3a进行氧化得到了化合物3a[BF4]并且测定了配合物3a、3b的电化学循环曲线；以配体1与配体3c反应,得到了脱硫的双核铁配合物4:[μ5-C5H5)2Fe2(C16N1O2S1)2]； (4)以3a[BF4]与NO反应得到了茂基侧面配位、NO桥联,以1,8-萘酰亚胺为配体的双核铁硫簇化合物5:[Cp*Fe(μ2-4,5-S2-R)(,μ-NO)FeCp*][BF4]； (5)以3a[BF4]与三乙基苄基氯化铵(TEBAC)反应,合成了茂基侧配位、三羰基端配位的1,8-萘酰亚胺类双核铁硫簇化合物6:[Cp*Fe(CO)2(μ2-4,5-S2-R)(CO)FeCp*]。以上产物通过1H NMR、IR、质谱、X-ray单晶衍射等分析表征手段确定了其结构。
[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.
【学位授予单位】：大连理工大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914.5

【共引文献】