Study On Synthesis And Catalytic Performance Of Tin(Ⅱ)metal Compounds

This paper mainly introduces six Sn(II)metal-organic complexes and one carbodiimide Li complex,including a penta-core Sn(II)complex 2a with guanidyl ligands,namely {NC[N(CH3)2)N(Ph)Sn Cl]}2Sn{NHC[N(CH3)2N(Ph)Sn Cl]}2,two 1,3,5-triazapentadienyl Sn(II)complexes 3a and 3b,namely(2-C5H4N)NC[N(CH3)2]N · Sn Cl,[(Si Me3)NC(C5H5N)NC(C5H5N)]Sn(C5H5N)2,three of which are α-diimines Sn(II)complexes 4a-4c which are ligands,namely [(2-C5H5N)C(NPh)(NSi Me3)] · Sn[Ph NC(2-C5H4N)(NSi Me3)],[(2-C5H5N)C(NSi Me3)] · Sn Cl,[(2-C5H5N)C(NAr)(NSi Me3)] · Sn Cl(Ar = 2,6-iPr2-C6H3)and a carbodiimide Li complex 5a,namely(Ar NCNLi · THF)4.Seven new organometallic compounds were synthesized.Their structures were characterized by 1H NMR,13 C NMR and X-ray single crystal diffraction,and their melting points were measured.Besides,the complexes 2a,3a,4a,4b,4c were used as catalysts to study the performance of aromatic amines and carbodiimides giving guanidine.The study of catalytic performance was mainly explored by changing the experimental temperature and reaction time,so as to develop better catalysts.This thesis included the following five chapters:Chapter 1: Introduction: The background and research methods of guanidine and its derivatives are mainly mentioned,as well as the significance and purpose of this thesis.Chapter 2: Synthesis of a new pentanuclear tin(Ⅱ)complex 2a with guanidyl as the ligand.The structure and melting point of 2a were characterized by 1H NMR,13 C NMR and X-ray single crystal diffraction.The complex 2a was used as a catalyst to investigate the catalytic performance of aromatic amines and carbodiimides forming guanidine.The optimal reaction condition for complex 2a as a catalyst was at 80 ℃ for 0.5 h.Chapter 3: Synthesis of two 1,3,5-triazapentadienyl Sn(Ⅱ)metal complexes 3a and 3b,namely(2-C5H4N)NC[N(CH3)2]NH · Sn Cl2,[(Si Me3)NC(C5H5N)NC(C5H5N)]Sn(C5H5N)2.Their structures were characterized by 1H NMR,13 C NMR and X-ray single crystal diffraction,and their melting points were measured.The complex 3a was used as a catalyst to investigate the catalytic performance of aromatic amine and carbodiimide for guanidine formation.Finally,the optimal reaction condition for the complex 3a as a catalyst was 25 minutes at 25 °C,and the yield reached 99.2 %.Chapter 4: Synthesis of three Sn(II)metal complexes 4a-4c with α-diimine as ligands,4a-4c was synthesized,characterized by 1H NMR,13 C NMR and X-ray single crystal diffraction,and its melting point was determined.Then,the complexes 4a-4c were used as catalysts to investigate the catalytic performance of aromatic amines and carbodiimides for guanidine formation.Finally,it was found that the catalytic effect for giving to guanidine is better when Ph NH2 and iPr N = C = NiPr as substrates,and both increasing the temperature and the reaction time can improve the catalytic effect,but complex 4b was a little special.The optimal reaction temperature was 50 ℃.The catalytic activity of complex 4b would be reduced when the temperature increased.There was almost no catalytic effect when using Ar NH2(Ar = 2,6-iPr2-C6H3)and iPr N=C=NiPr as substrates in a certain temperature and time range.Chapter 5: A new carbodiimide Li complex 5a was synthesized.Their structures were characterized by 1H NMR,13 C NMR and X-ray single crystal diffraction,and their melting points were measured.