화학공학소재연구정보센터
Inorganic Chemistry, Vol.47, No.2, 612-620, 2008
Insertion of CO2, ketones, and aldehydes into the C-LI bond of 1,3,5-triaza-7-phosphaadamantan-6-yllithium
The synthesis and structures of a series of new water-soluble phosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA) are described. Insertion of aldehydes or ketones into the C-Li bond of 1,3,5-triaza-7-phosphaadamantan-6-yllithium (PTA-Li) resulted in the formation of a series of slightly water-soluble beta-phosphino alcohols (PTA-CRR'OH, R = C6H5, C6H4OCH3, ferrocenyl; R' = H, C6H5, C6H4OCH3) derived from the heterocyclic phosphine PTA. Insertion of CO2 yielded the highly water-soluble carboxylate PTA-CO2Li, S-25 degrees approximate to 800 g/L. The compounds have been fully characterized in the solid state by X-ray crystallography and in solution by multinuclear NMR spectroscopy. The addition of PTA-Li to symmetric ketones results in a racemic mixture of PTA-CR2OH ligands with a single resonance in the P-31{H-1} NMR spectrum between -95 and -97 ppm. The addition of PTA-Li to aldehydes results in a mixture of diasteromeric compounds, PTA-CHROH, with two P-31{H-1} NMR resonances between -100 and -106 ppm. Three (eta(6) -arene)RuCl2(PTA-CRR'OH) complexes of these ligands were synthesized and characterized, with the ligands binding in a kappa(1) coordination mode. All the ligands and ruthenium complexes are slightly soluble in water with S-25 degrees = 3.9-11.1 g/L for the PTA-CRR'OH ligands and S-25 degrees = 3.3-14.1 g/L for the (eta(6) -arene)RUCl2(PTA-CRR'OH) complexes.