Diane Dickie - Synthesis and Properties of New (Phosphinoylmethyl)Pyridine N-Oxides.

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      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. Zeitschrift fuer   Anorganische und Allgemeine Chemie 639 (7)   1101-1116

      Abstract: Syntheses for   2-[1-(diarylphosphinoyl)-1-(pyridin-2-yl)methyl]pyridines, (8a,   b), and   2-[1-(diarylphosphinoyl)-1,1-bis(methylpyridin-2-yl)methyl]pyridines,   (11a, b), (Ar = C6H5 and 2-CF3C6H4), based on substitution of   2-methylpyridine fragments onto the exo methylene C atom of   2-[(diaryl)phosphinoylmethyl]pyridine platforms, are described.   N-oxidns. of 8a, b and 11a, b produced the   2-[1-(diarylphosphinoyl)-1-(1-oxy-pyridin-2-yl)methyl]pyridine   N-oxides (5a, b) and the   2-[1-(diarylphosphinoyl)-1,1-bis(1-oxy-methylpyridin-2-yl)methyl]pyridines   (6a, b), resp. The short-arm pyridine fragment of 11a, b resists   N-oxidn., and the fully oxidized mols.,   2-[1-(diarylphosphinoyl)-1,1-bis(1-oxy-methylpyridin-2-yl)methyl]pyridine   N-oxides (7a, b) were not isolated. Mol. mechanics calcns. 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)(NO3)3(MeOH)2]·CH2Cl2,   revealed a monodentate Er-O=P interaction. However, complexes   formed by a more sym. trifunctional   phenylphosphino-bis-2-methylpyridine N,N,P-trioxide ligand,   (meNO)2PO*, {La[(meNO)2PO*](OTf)2(MeOH)3(H2O)+}(OTf-) and   {Pr[(meNO)2PO*](OTf)(MeOH)4+}(OTf-)2, realized a tridentate   coordination mode. Solvent extn. behaviors for EuIII and AmIII in   HNO3 solns. using 5a, b, 6a, b, Ph3PO 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 behave more   like Ph3PO than 3a. [on SciFinder(R)]

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