Synthesis and f-element ligation properties of NCMPO-decorated pyridine N-oxide platforms

Journal Article · Wed Jan 01 00:00:00 EST 2014 · Dalton Transactions

DOI:https://doi.org/10.1039/c3dt53611d· OSTI ID:1131525

Ouizem, Sabrina ^[1]; Rosario-Amorin, Daniel ^[1]; Dickie, D. A. ^[1]; Paine, Robert T. ^[1]; De Bettencourt-Dias, Ana ^[2]; Hay, Benjamin ^[3]; Podair, Julien ^[3]; Delmau, Laetitia Helene ^[3]

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1. University of New Mexico, Albuquerque
2. University of Nevada, Reno
3. ORNL

Stepwise syntheses of 2-{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]C5H4NO (6), 2-{[2-(diphenylphosphoryl)acetamido]methyl}-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]-6-[Ph2P(O)CH2]C5H3NO (7) and 2,6-bis{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2,6-[Ph2P(O)CH2C(O)N(H)CH2]2C5H3NO (8), are reported along with spectroscopic characterization data and single crystal X-ray diffraction structure determination for 6 2H2O, 7 and 2,6-[Ph2P(O)CH2C(O)N(H)CH2]2C5H3N MeOH 18 MeOH, the pyridine precursor of 8. Molecular mechanics computations indicate that 6, 7 and 8 should experience minimal steric hindrance to donor group reorganization that would permit tridentate, tetradentate and pentadentate docking structures for the respective ligands on lanthanide cations. However, crystal structure determination for the lanthanide complexes, {[Yb(6)(NO3)3] (MeOH)}n, {[Lu(6)(NO3)3] (MeOH)}n, [Er(6)2(H2O)2](NO3)3 (H2O)4}n, {[La(13)(NO3)3(MeOH)] (MeOH)}n, {[Eu(7)(NO3)2(EtOAc)0.5(H2O)0.5](NO3)}2 MeOH and [Dy3(7)4(NO3)4(H2O)2](NO3)5 (MeOH)5 (H2O)2 reveal solid-state structures with mixed chelating/bridging ligand:Ln(III) interactions that employ lower than the maximal denticity. The binding of 6 and 7 with Eu(III) in the solid state and in MeOH solutions is also accessed by emission spectroscopy. The acid dependence for solvent extractions with 6 and 7 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions is described and compared with the behavior of n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (OPhDiBCMPO, 1b) and 2-[(diphenyl)phosphinoylmethyl]pyridine N-oxide (DPhNOPO, 4a).

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: DE-AC05-00OR22725
• OSTI ID: 1131525
• Journal Information: Dalton Transactions, Vol. 43, Issue 22; ISSN 1477--9226
• Country of Publication: United States
• Language: English