Synthesis And Characterization Of B And Si Compounds From Lithium Amides And α-H Free Nitriles And Li Compounds From Lithium Amides And Carbodiimides

In this paper,Ph N（Li）Si Me₃（L¹）,2,6-ⁱPr₂C₆H₃N（Li）Si Me₃（L²）,Li N（Si Me₃）₂（L³）were used as starting materials to react withα-H free nitriles such as dimethylcyanamide,1-piperidinecarbonitrile,2-cyanopyridine,3-cyanopyridine,and 4-cyanopyridine,and then metathesis reaction with Ph BCl₂ or Si Cl₄,to give 2 novel B（III）complexes 2a-2b and 6novel Si（IV）complexes 3a-3f.2,6-ⁱPr₂C₆H₃N（Li）Si Me₃（L²）was used as starting material to react withα-H free nitriles such as dimethylcyanamide,1-piperidinecarbonitrile and3-cyanopyridine,and then with carbodiimides,to give 4 novel Li（I）complexes 4a-4d.They were characterized and analyzed by X-ray single crystal diffraction,¹H NMR,¹³C NMR,⁷Li NMR,melting point measurement and elemental analysis.1:Using starting materials L¹ and L² to react with 2-cyanopyridine in the equal molar ratio,and then with Ph BCl₂ in the equal ratio give twoα-diimine B（Ⅲ）compounds 2a and2b.Their structures were characterized by X-ray single crystal diffraction,¹H NMR,¹³C NMR,melting point determination,and elemental analysis.2:Using starting materials L¹,L²,and L³ to react with 2-cyanopyridine,3-cyanopyridine and 4-cyanopyridine in the ratios of 1:1,and then with Si Cl₄ in the equal molar ratio give four amidinate Si（IV）compounds 3a-3d.Using starting materials L¹ and L² to react with dimethylcyanamide,1-piperidinonitrile in the ratios of 1:2,and then with Si Cl₄ in the equal molar ratio give two 1,3,5-triazapentadiene Si（IV）compounds 3e and 3f.Their structures were characterized by X-ray single crystal diffraction,¹H NMR,¹³C NMR,melting point determination,and elemental analysis.3:Using starting material L² to react with dimethylcyanamide,1-piperidinonitrile,3-cyanopyridine in the equal molar ratio in the presence of TMEDA,and then with N,N’-dicyclohexylcarbodiimide give three monomeric 1,3,5-triazapentadiene Li（I）compounds 4a-4c.Using starting material L² to react with 2-cyanopyridine in the equal molar ratio in the absence of TMEDA and then with N,N’-diisopropylcarbodiimide give a dimeric 1,3,5-triazapentadiene Li（I）compound 4d.Their structures were characterized by X-ray single crystal diffraction,¹H NMR,¹³C NMR,⁷Li NMR,melting point determination,and elemental analysis.