TY - JOUR
T1 - Synthesis and f-element ligation properties of NCMPO-decorated pyridine N-oxide platforms
AU - Ouizem, Sabrina
AU - Rosario-Amorin, Daniel
AU - Dickie, Diane A.
AU - Paine, Robert T.
AU - De Bettencourt-Dias, A.
AU - Hay, Benjamin P.
AU - Podair, Julien
AU - Delmau, Lætitia H.
PY - 2014/6/14
Y1 - 2014/6/14
N2 - Stepwise syntheses of 2-{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]C 5H4NO (6), 2-{[2-(diphenylphosphoryl)acetamido]methyl}-6- [(diphenylphosphoryl)methyl]pyridine 1-oxide, 2-[Ph2P(O)CH 2C(O)N(H)CH2]-6-[Ph2P(O)CH2]C 5H3NO (7) and 2,6-bis{[2-(diphenylphosphoryl)acetamido] methyl}pyridine 1-oxide, 2,6-[Ph2P(O)CH2C(O)N(H)CH 2]2C5H3NO (8), are reported along with spectroscopic characterization data and single crystal X-ray diffraction structure determination for 6·2H2O, 7 and 2,6-[Ph 2P(O)CH2C(O)N(H)CH2]2C 5H3N·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)(NO 3)3(MeOH)]·(MeOH)}n, {[Eu(7)(NO 3)2(EtOAc)0.5(H2O) 0.5](NO3)}2·MeOH and [Dy 3(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).
AB - Stepwise syntheses of 2-{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]C 5H4NO (6), 2-{[2-(diphenylphosphoryl)acetamido]methyl}-6- [(diphenylphosphoryl)methyl]pyridine 1-oxide, 2-[Ph2P(O)CH 2C(O)N(H)CH2]-6-[Ph2P(O)CH2]C 5H3NO (7) and 2,6-bis{[2-(diphenylphosphoryl)acetamido] methyl}pyridine 1-oxide, 2,6-[Ph2P(O)CH2C(O)N(H)CH 2]2C5H3NO (8), are reported along with spectroscopic characterization data and single crystal X-ray diffraction structure determination for 6·2H2O, 7 and 2,6-[Ph 2P(O)CH2C(O)N(H)CH2]2C 5H3N·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)(NO 3)3(MeOH)]·(MeOH)}n, {[Eu(7)(NO 3)2(EtOAc)0.5(H2O) 0.5](NO3)}2·MeOH and [Dy 3(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).
UR - http://www.scopus.com/inward/record.url?scp=84900534669&partnerID=8YFLogxK
U2 - 10.1039/c3dt53611d
DO - 10.1039/c3dt53611d
M3 - Article
AN - SCOPUS:84900534669
SN - 1477-9226
VL - 43
SP - 8368
EP - 8386
JO - Dalton Transactions
JF - Dalton Transactions
IS - 22
ER -