Synthesis And Characterization Of Five-membered Heterocycle-derived Bidentate Ligands And Their Manganese And Palladium Complexes

Five-membered heterocycle is a kind of compound with a uniquestructure with alone pair of electrons on the hetero atom. Thesecompounds can be used to synthesize bidentate and polydentateligands with diverse and stable structure. It is of particular interestowing to its ability of better coordination, so that it can be used asligands and coordinated with metal ions to obtain metal complexes,which exibit unique chemical properties and structure. In this thesis,a series of five-membered heterocycle-derived bidentate ligands weredesigned and synthesized. The manganese and palladium complexeswere explored preliminarily. The main works are as follows:1. Substrates1a-b reacted with2-bromide thiazole/thiophene toproduce the correspording compounds2-(3,5-disubstituted-1,2,4-diazaphosphole) thiazole2a-b and2-(3,5-disubstituted-1,2,4-diazaphosphole)thiophene3a-b. The reaction of1a-d with4-chloromethyl thiazole hydrochloride were carried out, which givethe correspording product2-[(3,5-disubstituted-1,2,4-diazaphosphole)-4-methylene] thiazole4a-d. These compounds havebeen fully characterized by NMR, melting points. Additionally, the molecuar structure of compounds2a,3a,4a and4c were comfirmedby X-ray crystallography.2. The synthesis of2-[(3,5-disubstituted-1,2,4-diazaphosphole)-2-carbonyl] furan5a-d was achieved by the reaction of1a-b with2-furoyl chloride. A series of2-[(3,5-disubstituted-1,2,4-diazaphosphole)-2-carbonyl]thiophene6a-d were synthesized bythe reaction between1a-d and2-thenoyl chloride. Thesecompounds have been characterized by, NMR, melting point and themolecuar structure of compounds5d and6d were comfirmed by X-raycrystallography.3. The coordination chemistry of manganese and palladium withnovel bidentate ligands were explored preliminary. The manganesecomplexes Ⅰ and Ⅱ were synthesized by the reaction of compounds2a and4a with MnCl2. Compounds6c and6d reacted withPd(CH3CN)2Cl2to prepare the palladium complexes Ⅲ and Ⅳ.These new metal complexes were obtained by experimentalphenomena, IR and solubility.