Wong Gene W, Lee Wei-Chih, Frost Brian J
Department of Chemistry, MS 216, University of Nevada, Reno, Nevada 89557, USA.
Inorg Chem. 2008 Jan 21;47(2):612-20. doi: 10.1021/ic701936x. Epub 2007 Dec 22.
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, C(6)H(4)OCH(3), ferrocenyl; R' = H, C(6)H(5), C(6)H(4)OCH(3)) derived from the heterocyclic phosphine PTA. Insertion of CO(2) yielded the highly water-soluble carboxylate PTA-CO(2)Li, S(2)5 degrees approximately 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-CR(2)OH ligands with a single resonance in the (31)P{(1)H} 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 (31)P{(1)H} NMR resonances between -100 and -106 ppm. Three (eta(6)-arene)RuCl(2)(PTA-CRR'OH) complexes of these ligands were synthesized and characterized, with the ligands binding in a kappa1 coordination mode. All the ligands and ruthenium complexes are slightly soluble in water with S25 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)RuCl(2)(PTA-CRR'OH) complexes.
描述了一系列基于1,3,5-三氮杂-7-磷杂金刚烷（PTA）的新型水溶性膦配体的合成与结构。醛或酮插入1,3,5-三氮杂-7-磷杂金刚烷-6-基锂（PTA-Li）的C-Li键中，形成了一系列由杂环膦PTA衍生的微溶于水的β-膦基醇（PTA-CRR'OH，R = C6H5、C(6)H(4)OCH(3)、二茂铁基；R' = H、C(6)H(5)、C(6)H(4)OCH(3)）。插入CO(2)得到高水溶性的羧酸盐PTA-CO(2)Li，25℃时的溶解度约为800 g/L。这些化合物已通过X射线晶体学在固态下以及通过多核NMR光谱在溶液中进行了全面表征。将PTA-Li添加到对称酮中会产生PTA-CR(2)OH配体的外消旋混合物，在(31)P{(1)H} NMR光谱中有一个-95至-97 ppm之间的单共振。将PTA-Li添加到醛中会产生非对映异构体化合物PTA-CHROH的混合物，在-100至-106 ppm之间有两个(31)P{(1)H} NMR共振。合成并表征了这些配体的三种(η(6)-芳烃)RuCl(2)(PTA-CRR'OH)配合物，配体以κ1配位模式结合。所有配体和钌配合物在水中微溶，PTA-CRR'OH配体在25℃时的溶解度为3.9 - 11.1 g/L，(η(6)-芳烃)RuCl(2)(PTA-CRR'OH)配合物在25℃时的溶解度为3.3 - 14.1 g/L。
