Synthesis And Catalytic Performance Of Amidinate And1,3,5-Triazapentadienyl Metal Complexes

In this work, different amidino and guanidino ligands were obtained via the addition reaction between a variety of a-hydrogen-free nitriles and derivatives of Cyclohexylamine and bis(trimethylsilyl) amine (CyN(Li)SiMe3, LiN(SiMe3)2). On the basis of this, the ligands was reacted with a variety of metal chlorides to obtain corresponding organometallic compounds whose crystal structures and chemical and physical properties were studied systematicly. Six novel organometallic compounds were studied in this paper. Their structures were characterized by single crystal X-ray diffraction,1H NMR,13C NMR spectra and elemental analysis. The main contents of this work include three chapters:Chapter1. The chapter1is a detailed introduction about purpose, significance and background of our work. The main contents are as follows:(1) the summary of science of organometallic chemistry;(2) synthesis methods, research progress and applications of amidino-organometallic compounds;(3) synthesis methods, research progress and prospect of guanidine-organometallic compounds.Reagents and congditions:i PhCN, Et2O, ca,-78℃;1/3ZrCl4, Et2O, ca,-78℃. ii PhCN, Et2O, ca,-78℃;1/2ZrCl4, Et2O, ca,-78℃.Chapter2. CyN(Li)SiMe3(Cy=cyclohexyl) were used as materials to react with a-Hydrogen-free benzonitriles in ratio of1:1. The obtained ligands were reacted in the ratio of2:1and3:1respectively with anhydrous ZrCl4in the solvent of ether to obtain2a and2b. It should be noticed that the obtained ligands was dropwise added into the anhydrous ZrCl4solution of ether to react in the ratio of2:1which was different with the reaction between them in the ratio of3:1. The synthetic route is showed in scheme1. The structure of2a and2b were characterized by single crystal X-ray diffraction,1H NMR,13C NMR. spectra and elemental analysis.Reagents and congditions:i2Me2NCN, Et2O, ca,-78℃;1/2CdCl2·2.5H2O, Et2O, ca,-78℃. ii2Me2NCN, Et2O, ca,-78℃;1/2MnCl2, Et2O, ca,-78℃. iii2Me2NCN, Et2O, ca,-78℃;1/2CoCl2, Et2O, ca,-78℃. iv2Me2NCN, Et2O, ca.-78℃;1/2SnCl4, Et2O,ca,-78℃.Chapter3. The guanidino ligands were obtained from the addition reaction between LiN(SiMe3)2ligands and a-Hydrogen-free Me2NCN. An unexpected product3a was obtained when the guanidino ligands is reacted with CdCl2·2.5H2O.3b was obtained from the reaction between guanidino ligands and CoCl2.3c was obtained from the reaction between guanidino ligands and MnCl2in the way of dropwise added.3d was obtained from the reaction between guanidino ligands and SnCl4.The synthetic route of the compounds obtained above is showed in scheme2. Four obtained compounds are all in U conformation. Their structures were characterized by single crystal X-ray diffraction,1H NMR,13C NMR spectra and elemental analysis.