Synthesis of the Novel Multidentate Ligand and Its Mono- and Di-nuclear Ruthenium Complex for Cyanation of Tertiary Amines
Date Issued
2011
Date
2011
Author(s)
Lo, Ying-Hao
Abstract
We have successfully prepared 2,8-di(2-pyridyl)-5-phenyl-l,9,10-anthyridine (4a), which is a multidentate ligand. For the ligand synthesis, the double Friedlander condensations of 2,6-diamino-4-phenylpyridine-3,5-dicarboxaldehyde (3) with 2-acetylpyridine yielded 4a. Coordination of 4a with two kinds of ruthenium precursor, RuCl2(CO)3(THF) and [(η6-p-cymene)RuCl2]2 , resulted in the formatioon of a mono-nuclearspecies ([(4a)Ru(CO)3Cl)(Ru(Cl)3(CO)3]) (Ru1) and a dinuclear ruthenium complex ([(4a)Ru2(p-cymene)2(Cl)2][(PF6)(Cl)]) (Ru2), respectively. Two complexes were characterized by X-ray crystals, NMR, ESI-MASS. We had found that one of the p-cymene of Ru2 is fluxional, and we proposed that the p-cymene might vibrate when Ru2 is dissolved in solvent. The vibrate frequency and free energy was determined by the low-temperature 1H NMR experiment.
In the catalytic application, mono- and di-nuclear ruthenium complexes were active for the cyanation of tertiary amines with sodium cyanide. Complex Ru2 afforded the corresponding a-aminonitriles with good yields with hydrogen peroxide as the oxidant under acidic condition.
Subjects
Di-nuclear Ruthenium Complex
Multidentate Ligand
Cyanation of Tertiary Amines
Type
thesis
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