【摘要】：五元雜環(huán)是一類具有獨特結(jié)構(gòu)的化合物，其雜原子具有孤對電子，使此類化合物能夠形成結(jié)構(gòu)多樣的雙齒、多齒配體，此類配體具有較好的配位能力，能與多種金屬試劑反應(yīng)制備結(jié)構(gòu)穩(wěn)定、性能優(yōu)良的金屬配合物。本論文主要研究了五元雜環(huán)衍生雙齒配體的合成及其與金屬錳、鈀的配位化學(xué)反應(yīng)。具體工作如下： 1.化合物1a-b分別與2-溴噻唑/噻吩反應(yīng)，合成2-(3,5-二取代基-1,2,4-二唑膦基)噻唑（R=H,i-Pr）2a-b和2-(3,5-二取代基-1,2,4-二唑膦基)噻吩（R=H,i-Pr）3a-b；以1a-d為原料，與4-氯甲基噻唑鹽酸鹽反應(yīng)，合成新化合物2-[(3.5-二取代基-1.2.4-二唑膦基)-4-亞甲基]噻唑（R=H, i-Pr，Ph，t-Bu）4a-d。并通過熔點、核磁共振、X-單晶衍射等手段對這些新化合物進行結(jié)構(gòu)表征。 2.化合物1a-d為原料，與呋喃-2-甲酰氯反應(yīng)，合成羰基橋連的2-[(3.5-二取代基-1.2.4-二唑膦基)-2-羰基]呋喃（R=H, i-Pr，Ph，t-Bu）5a-d；與噻吩-2-甲酰氯反應(yīng)，合成2-[(3.5-二取代基-1.2.4-二唑膦基)-2-羰基]噻吩（R=H, i-Pr，Ph，t-Bu）6a-d，，并通過熔點、核磁共振、X-單晶衍射等手段對新化合物進行表征。 3.初步探索五元雜環(huán)衍生雙齒配體與金屬錳、鈀的配位化學(xué)。以2a、4a為配體，與錳試劑反應(yīng)合成錳配合物Ⅰ、Ⅱ；以6c、6d為配體，與鈀試劑反應(yīng)制備鈀配合物Ⅲ、Ⅳ。通過實驗現(xiàn)象變化、紅外測試以及產(chǎn)物溶解性可以證實雙齒配體與金屬錳、鈀反應(yīng)得到了相應(yīng)的配合物。
[Abstract]:Quaternary heterocyclic compounds are a class of compounds with unique structure. Their heteratoms have solitary pairs of electrons, which enable them to form didentate and polydentate ligands with various structures, and such ligands have good coordination ability. Metal complexes with stable structure and excellent properties can be prepared by reaction with various metal reagents. In this paper, the synthesis of didentate ligands derived from quaternary heterocyclic derivatives and their coordination reactions with manganese and palladium were studied. The specific work is as follows: 1. The compound 1a-b was reacted with 2-bromothiazole / thiophene to synthesize 2- (3o 5-disubstituted -1- (2-triazophosphonyl) thiazolyl) 2a-b and 2- (3O5- disubstituted -1-dithiophene) 2a-b, respectively. 4- diazophosphonyl) thiophene (RX Hni-Pr) 3a-b; A new compound 2- [(3.5- disubstituted-1.2.4- diazophosphonyl) -4-methylene] thiazole (RH-, i-Pranpho) was synthesized from 1a-d and 4-chloromethylthiazole hydrochloride. T-Bu) 4a-d. The structures of these new compounds were characterized by melting point, NMR and X-single crystal diffraction. 2. Carbonyl bridged 2- [(3.5-disubstituted -1.2.4-diazophosphonyl) -2-carbonyl] furan (RHH, i-PrPh) was synthesized by the reaction of compound 1a-d with furan-2-formyl chloride. T-Bu) 5a-d; The reaction of thiophene-2-formyl chloride with 2- [(3.5- disubstituted-1.2.4-diazophosphonyl) -2-carbonyl] thiophene (RH, i-Pr-Phnt-Bu) 6a-dwas synthesized by means of melting point, nuclear magnetic resonance (NMR). The new compounds were characterized by X-single crystal diffraction. 3. The coordination chemistry of didentate ligands derived from quaternary heterocyclic derivatives with manganese and palladium was preliminarily investigated. Manganese complexes 鈪

本文編號：2332507