Synthesis and coordination properties of trifluoromethyl decorated derivatives of 2,6-bis[(diphenylphosphinoyl)methyl]pyridine N-oxide ligands with lanthanide ions.
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.
Pailloux
Sylvie
S
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
Shirima
Cornel Edicome
CE
Ray
Alisha D
AD
Duesler
Eileen N
EN
Paine
Robert T
RT
Klaehn
John R
JR
McIlwain
Michael E
ME
Hay
Benjamin P
BP
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*
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