title: Synthesis and coordination properties of trifluoromethyl decorated derivatives of 2,6-bis[(diphenylphosphinoyl)methyl]pyridine N-oxide ligands with lanthanide ions.
abstract: Phosphinoyl Grignard-based substitutions on 2,6-bis(chloromethyl)pyridine followed by N-oxidation of the intermediate 2,6-bis(phosphinoyl)methylpyridine compounds with mCPBA give the target trifunctional ligands 2,6-bis[bis(2-trifluoromethylphenyl)phosphinoylmethyl]pyridine 1-oxide (2a) and 2,6-bis[bis(3,5-bis(trifluoromethyl)phenyl)phosphinoylmethyl]pyridine 1-oxide (2b) in high yields. The ligands have been spectroscopically characterized, the molecular structures confirmed by single crystal X-ray diffraction methods, and the coordination chemistry surveyed with lanthanide nitrates. Single crystal X-ray diffraction analyses are described for the coordination complexes Nd(2a)(NO(3))(3), Nd(2a)(NO(3))(3) x (CH(3)CN)(0.5), Eu(2a)(NO(3))(3), and Nd(2b)(NO(3))(3) x (H(2)O)(1.25); in each case the ligand binds in a tridentate mode to the Ln(III) cation. These structures are compared with the structures found for lanthanide coordination complexes of the parent NOPOPO ligand, [Ph(2)P(O)CH(2)](2)C(5)H(3)NO.
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
authors.forename: Sylvie
authors.initials: S
authors.lastname: Pailloux
authors.forename: Cornel Edicome
authors.initials: CE
authors.lastname: Shirima
authors.forename: Alisha D
authors.initials: AD
authors.lastname: Ray
authors.forename: Eileen N
authors.initials: EN
authors.lastname: Duesler
authors.forename: Robert T
authors.initials: RT
authors.lastname: Paine
authors.forename: John R
authors.initials: JR
authors.lastname: Klaehn
authors.forename: Michael E
authors.initials: ME
authors.lastname: McIlwain
authors.forename: Benjamin P
authors.initials: BP
authors.lastname: Hay
mesh_terms: D018360:Crystallography, X-Ray; D003497:Cyclic N-Oxides / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
chemical_list: C540720:2,6-bis((diphenylphosphinoyl)methyl)pyridine N-oxide; D003497:Cyclic N-Oxides; D007477:Ions; D028581:Lanthanoid Series Elements; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines