1449196-49-9Relevant academic research and scientific papers
Synthesis and properties of new (Phosphinoylmethyl)pyridine N-oxides
Pailloux, Sylvie L.,Rosario-Amorin, Daniel,Chakravarty, Manab,Camus, Jean-Michel,Smith, Karen Ann,Duesler, Eileen N.,Dickie, Diane A.,Paine, Robert T.,Klausmeyer, Kevin K.,Padron, Daniel A.,Hay, Benjamin P.,Delmau, Laetitia H.
, p. 1101 - 1116 (2013/07/27)
Syntheses for 2-[1-(diarylphosphinoyl)-1-(pyridin-2-yl)methyl]pyridines, (8a, b), and 2-[1-(diarylphosphinoyl)-1, 1-bis(methylpyridin-2yl)methyl] pyridines, (11a, b), (Ar = C6H5 and 2-CF3C 6H4), based on substitution of 2-methylpyridine fragments onto the exo methylene carbon atom of 2-[(diaryl)phosphinoylmethyl]pyridine platforms, are described. N-oxidations of 8a, b and 11a, b produced the 2-[1-(diarylphosphinoyl)-1-(1-oxy-pyridin-2yl)methyl]pyridine N-oxides (5a, b) and the 2-[1-(diarylphosphinoyl)-1, 1-bis(1-oxy-methylpyridin-2-yl)methyl] pyridines (6a, b), respectively. The short-arm pyridine fragment of 11a, b resists N-oxidation, and the fully oxidized molecules, 2-[1-(diarylphosphinoyl)-1, 1-bis(1-oxy-methylpyridin-2-yl)methyl]pyridine N-oxides (7a, b) were not isolated. Molecular mechanics calculations for gas phase 1:1 ligand/lanthanide complexes indicated that 5a should accommodate a tridentate NO(meNO)PO coordination mode with minimal steric strain. In contrast, 7a cannot form tetradentate NO(meNO)2PO chelates; however, tridentate binding should be accessible with minimal ligand strain. Coordination complexes of 8a, b, 5a, b, 6a, b and 11a, b with Ln(NO3)3 salts were isolated and a X-ray crystal structure for [Er(8a)(NO 3)3(MeOH)2]·CH2Cl 2, revealed a monodentate Er-O=P interaction. On the other hand, complexes formed by a more symmetrical trifunctional phenylphosphino-bis-2- methylpyridine N, N, P-trioxide ligand, (meNO)2PO*, {La[(meNO)2PO*)](OTf)2(MeOH)3(H 2O)+}(OTf-) and {Pr[(meNO)2PO* )](OTf)(MeOH)4+}(OTf-)2, realized a tridentate coordination mode. Solvent extraction behaviors for EuIII and AmIII in nitric acid solutions using 5a, b, 6a, b, Ph 3PO and the parent bifunctional ligand 2-[(diphenylphosphanyl)methyl] pyridine N, P-dioxide (3a) in 1, 2-dichloroethane were assessed, and 5a, b and 6a, b were found to behave more like Ph3PO than 3a. Copyright
