76645-88-0Relevant articles and documents
The influence of the second and outer coordination spheres on Rh(diphosphine)2 CO2 hydrogenation catalysts
Bays, J. Timothy,Priyadarshani, Nilusha,Jeletic, Matthew S.,Hulley, Elliot B.,Miller, Deanna L.,Linehan, John C.,Shaw, Wendy J.
, p. 3663 - 3670 (2014)
A series of [Rh(PCH2XRCH2P)2]+ complexes was prepared to investigate second and outer coordination sphere effects on CO2 hydrogenation catalysis, where X is CH2 (dppp) or X-R is N-CH3, N-CH2COOH (glycine), N-CH2COOCH3 (Gly-OMe), or N-CH2C(O)N-CH(CH3)COOCH3 (GlyAla-OMe). All of these complexes were active for CO2 reduction to formate, with the N-CH3 derivative offering an 8-fold enhancement over the dppp derivative, which is consistent with increased electron density around the metal. Despite the increase in rate with the addition of the pendant nitrogen, the addition of electron withdrawing amino acids and dipeptides to the amine resulted in complexes with reductions in rate of 1 to 2 orders of magnitude, most consistent with a change in pKa of the pendant amine, resulting in lower activity. Collectively, the data suggest multiple contributions of the pendant amine in this catalytic system.
Tricarbonylrhenium(I) complexes of phosphine-derivatized amines, amino acids and a model peptide: Structures, solution behavior and cytotoxicity
Zhang, Jianyong,Vittal, Jagadese J.,Henderson, William,Wheaton, Jessica R.,Hall, Iris H.,Hor, T.S.Andy,Yan, Yaw Kai
, p. 123 - 132 (2007/10/03)
Modified Mannich reactions of amines, amino acids and a model peptide with Ph2PH and CH2O gave bis(disphenylphosphinomethyl) amines(Ph2PCH2)2NR [R = Ph (1), CH2CH2OH(2), CH2COOCH2Ph (3), CH2CONHCH2COOCH2Ph (4). CH2COOH (5)] and [ReBr(CO)3(Ph2PCH2)2NCH 2]2 (12). All new complexes have been characterized by NMR and IR spectroscopy and for 7, 9 and 10, single-crystal X-ray diffraction analyses. Electrospray mass spectrometric studies show that the rhenium-phosphine chelates are very stable especially in neutral methanolic solution. Hydrolysis of the ester and amide linkages slowly occur in acidic and basic solutions over several weeks; displacement of the bromide ligand also occurs in basic medium. Cytotoxicity testing of 7-10 and 12 showed that all the complexes are active againts specific tumor cell lines, especially MCF-7 breast cancer and HeLa-S3 suspended eturine carcinoma.
OPTISCH AKTIVE N-PHOSPHINOMETHYLIERTE α-AMINOSAEUREN: SYNTHESE UND ANWENDUNG ALS LIGANDEN IN ASYMMETRISCHEN HYDRIERUNGEN MIT RHODIUM-KOMPLEXEN
Kellner, K.,Tzschach, A.,Nagy-Magos, A.,Marko, L.
, p. 307 - 314 (2007/10/02)
α-Aminoacids, their esters and sodium salts may be transformed by a modified Mannich-reaction into N-phosphinomethyl or N,N-bis(phosphinomethyl) derivatives.The sodium or triethylammonium salts of the chiral bisphosphines L-(-)-N,N-bis(diphenylphosphinomethyl)-alanine and -valine may be used as ligands to form enantioslective hydrogenation catalysts with rhodium complexes.The highest optical yield achieved was 29percent.
