五元杂环衍生双齿配体及其锰、钯配合物的合成与结构表征

发布时间：2018-11-15 07:08

【摘要】：五元杂环是一类具有独特结构的化合物，其杂原子具有孤对电子，使此类化合物能够形成结构多样的双齿、多齿配体，此类配体具有较好的配位能力，能与多种金属试剂反应制备结构稳定、性能优良的金属配合物。本论文主要研究了五元杂环衍生双齿配体的合成及其与金属锰、钯的配位化学反应。具体工作如下： 1.化合物1a-b分别与2-溴噻唑/噻吩反应，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为原料，与4-氯甲基噻唑盐酸盐反应，合成新化合物2-[(3.5-二取代基-1.2.4-二唑膦基)-4-亚甲基]噻唑（R=H, i-Pr，Ph，t-Bu）4a-d。并通过熔点、核磁共振、X-单晶衍射等手段对这些新化合物进行结构表征。 2.化合物1a-d为原料，与呋喃-2-甲酰氯反应，合成羰基桥连的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；与噻吩-2-甲酰氯反应，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，，并通过熔点、核磁共振、X-单晶衍射等手段对新化合物进行表征。 3.初步探索五元杂环衍生双齿配体与金属锰、钯的配位化学。以2a、4a为配体，与锰试剂反应合成锰配合物Ⅰ、Ⅱ；以6c、6d为配体，与钯试剂反应制备钯配合物Ⅲ、Ⅳ。通过实验现象变化、红外测试以及产物溶解性可以证实双齿配体与金属锰、钯反应得到了相应的配合物。
[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

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