【摘要】：席夫堿是一類(lèi)重要的含N化合物,其亞胺基團(tuán)(-C=N-)中的N上含有孤對(duì)電子,可以與大部分金屬離子形成穩(wěn)定的配合物。一些雙齒席夫堿可以通過(guò)[N,N]、[N,O]、[N,C]、[N,S]與金屬離子進(jìn)行配位,構(gòu)建出豐富的空間結(jié)構(gòu),使得席夫堿及其配合物具有各種性質(zhì)與功能,在醫(yī)學(xué)、催化、傳感、光學(xué)等領(lǐng)域有著廣泛的應(yīng)用。本文利用水楊醛與對(duì)苯二胺、聯(lián)苯胺、鄰聯(lián)甲苯胺、4,4′-二氨基二苯甲烷反應(yīng),構(gòu)建出一系列雙齒席夫堿。利用此類(lèi)席夫堿含有雙官能團(tuán)的結(jié)構(gòu)(含-OH,-C=N-),通過(guò)[N,O]與金屬離子銠、銥配位,構(gòu)建出一系列席夫堿橋聯(lián)的雙核銠、銥等配合物,為以后合成大環(huán)類(lèi)銠、銥配合物做了前期工作。本文首先合成了具有O,N-給體的雙齒席夫堿[{(2-OH)C6H4CH=N}2R]{R=C6H4,L1;R=(C6H4)2,L2;R=(o-MeC6H3)2,L3;R=(C6H4)2CH2,L4},通過(guò)紫外可見(jiàn)光譜和熒光光譜測(cè)試了它們?cè)诓煌軇┫碌墓庾V性質(zhì)。通過(guò)對(duì)L1、L2、L3、L4熔點(diǎn)、紅外光譜、核磁氫譜的測(cè)定和對(duì)化合物L(fēng)1單晶結(jié)構(gòu)的測(cè)試,證實(shí)得到了一系列水楊醛衍生的雙席夫堿。其次,合成了氯橋聯(lián)銠、銥配合物[Cp*MCl2]2(M=Rh,1;Ir,2),然后讓其與席夫堿進(jìn)行反應(yīng)生成雙核的銠、銥配合物。實(shí)驗(yàn)時(shí)先把水楊醛類(lèi)席夫堿加入甲醇溶劑中與氫氧化鈉反應(yīng)除去酚羥基的氫,形成活潑的O-離子;把配合物1、2分別溶解在CH2Cl2溶劑中,過(guò)濾至上述反應(yīng)中,合成了半夾心結(jié)構(gòu)的銠、銥配合物[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2C6H4](M=Rh,1a;Ir,1b),[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2(C6H4)2](M=Rh,2a;Ir,2b),[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2(o-MeC6H3)2](M=Rh,3a;Ir,3b),[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2(C6H4)2CH2](M=Rh,4a;Ir,4b)我們將以上所得的配合物1a,2a,3a,4a;1b,2b,3b,4b均作了紅外光譜和核磁氫譜的測(cè)定,并對(duì)特征峰進(jìn)行了歸屬。此外,我們還對(duì)配合物1a進(jìn)行了X-射線(xiàn)單晶衍射表征,通過(guò)晶體數(shù)據(jù)的研究,確認(rèn)我們合成出了一系列新型的雙核銠、銥配合物。此類(lèi)配合物易溶于二氯甲烷和氯仿等有機(jī)溶劑中,為研究此類(lèi)配合物各種性質(zhì)提供了有利條件。同時(shí)我們通過(guò)改變席夫堿配體鏈的長(zhǎng)短對(duì)雙核類(lèi)銠、銥配合物的空間結(jié)構(gòu)進(jìn)行調(diào)控,這對(duì)一系列新型的大環(huán)類(lèi)銠、銥配合物的構(gòu)筑,提供了很好的模板,具有廣闊的研究前景。
[Abstract]:Schiff base is an important class of N-containing compounds. The N of the iminodium group (-Cn-) contains solitary pairs of electrons, which can form a stable complex with most metal ions. Some didentate Schiff bases can be coordinated with metal ions by [Nn], [No], [NZC], [NZS], and form rich spatial structures, which make Schiff bases and their complexes have various properties and functions. In medicine, catalysis, sensing, optics and other fields have a wide range of applications. In this paper, a series of didentate Schiff bases were synthesized by the reaction of salicylaldehyde with p-phenylenediamine, benzidine, o-bimethylaniline, 4o 4- diaminodiphenylmethane. A series of binuclear rhodium and iridium complexes bridged by Schiff bases were synthesized by [Nino O] coordination with metal ions rhodium and iridium (including-OH,-C=N-), which were used for the synthesis of macrocyclic rhodium, and the structure of Schiff base containing bifunctional groups (including-OH,-C=N-) was used to construct a series of binuclear rhodium and iridium complexes bridged by Schiff bases. The iridium complex has done the preliminary work. In this paper, we first synthesized the didentate Schiff base with ON- donor [{(2-OH) C6H4CH=N} 2R] {RZC _ 6H _ 4N _ L _ 1C ~ (1 +) R = (C6H4) _ 2C _ (2) L _ (2N) R = (o-MeC6H3) ~ (2) L _ (3); R = (C6H4) 2CH _ 2C _ 4}. Their spectral properties in different solvents were measured by UV-Vis and fluorescence spectra. A series of bis Schiff bases derived from salicylidene aldehyde have been obtained by the determination of melting point, infrared spectrum, nuclear magnetic hydrogen spectrum and single crystal structure of compound L1. Secondly, chlorine-bridged rhodium and iridium complexes [Cp*MCl2] 2 (Cp*MCl2 1, Ir2) were synthesized, and then reacted with Schiff base to form binuclear rhodium and iridium complexes. In the experiment, salicylic aldehyde Schiff base was added into methanol solvent to react with sodium hydroxide to remove phenolic hydroxyl hydrogen to form active O- ion. The complex 1t2 was dissolved in the CH2Cl2 solvent and filtered into the above reaction. The semi-sandwich rhodium and iridium complexes [(Cp*MCl) 2 {NnO- 魏 2- (2-O) C6H4CH=N} 2C6H4] (Mnrh 1 a) were synthesized. (Ir,1b), [(Cp*MCl) 2 {NGUO- 魏 2- (2-O) C6H4CH=N} 2 (C6H4) 2], [(Cp*MCl) 2 {NGUO- 魏 2- (2-O) C6H4CH=N} 2 (o-MeC6H3) 2] (Mnhh 3aa), [(Cp*MCl) 2 {NGUO- 魏 2- (2-O) C6H4CH=N} 2 (o-MeC6H3) 2], [(Cp*MCl) 2 {NGO- 魏 2- (2-O) C6H4CH=N} 2 (o-MeC6H3) 2]; (Ir,3b), [(Cp*MCl) 2 {NO- 魏 2- (2-O) C6H4CH=N} 2 (C6H4) 2CH2] The infrared spectra and nuclear magnetic hydrogen spectra were measured for 1b ~ (2) b ~ (2) B ~ (3) B ~ (4) and the characteristic peaks were assigned. In addition, the complex 1a has been characterized by X-ray single crystal diffraction, and a series of new binuclear rhodium and iridium complexes have been synthesized by the study of crystal data. These complexes are easily soluble in organic solvents such as dichloromethane and chloroform, which provides favorable conditions for studying the properties of these complexes. At the same time, we regulate the spatial structure of binuclear rhodium and iridium complexes by changing the length of Schiff base ligand, which provides a good template for the construction of a series of new macrocyclic rhodium and iridium complexes, and has a broad research prospect.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.1

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