CHELATING PROPERTIES OF 2-((DIPHENYLPHOSPHINO)METHYL)PYRIDINE N,P-DIOXIDE AND 2,6-BIS((DIPHENYLPHOSPHINO)METHYL)PYRIDINE N,P,P'-TRIOXIDE TOWARD F-ELEMENT IONS

The bifunctional 2-((diphenylphosphino)methyl)pyridine NP-dioxide, 2-[ (C6H5)2P(O)CH2]C5H4NO (4), and trifunctional 2,6-bis((diphenylphosphin o)methyl)pyridine NPP'-trioxide, 2,6-[(C6H5)2P(O)CH2]2C5H3NO (5), liga nds have been prepared, and their coordination chemistry has been surv eyed with Pr(III), Tb(III), Yb(III), and Th(IV). Single-crystal X-ray diffraction analyses have been completed for several complexes. Crysta llographic data for [Tb(4)43+][(NO3)3(H2O)(EtOH)3-]: C74H72N7019P4Tb, orthorhombic, space group Pbca, a = 26.655(5) angstrom, b = 25.738(5) angstrom, c = 20.821(5) angstrom, z = 8, v = 14,284(5) angstrom3; stru cture refined to R(F) = 6.24% and R(wF) = 5.07% on 7068 data with F > 3sigma(F). The four ligands 4 produce a square antiprismatic coordinat ion polyhedron. Crystallographic data for [Pr(4)2(NO3)3].Et2O.1/2 MeOH : C40.5H44N5014.5P2Pr, triclinic, space group P1BAR, a = 11.02(5) angs trom, b = 11.802(12) angstrom, c = 18.560(4) angstrom, alpha = 96.70(2 )-degrees, beta = 95.84(3)-degrees, gamma = 108.55(3)-degrees, Z = 2, V = 2247.9(12) angstrom3; structure refined to R(F) = 6.80% and R(wF) = 5.65% on 4561 data with F > 2sigma(F). The Pr(III) is bonded to two bidentate ligands and three nitrate ions. Crystallographic data for [Y b(5)(NO3)3].MeOH: C32H31N4O13P2Yb, monoclinic, space group P2(1)/n, a = 11.677(2) angstrom, b = 15.764(3) angstrom, c = 20.242(3) angstrom, beta = 100.18(l)-degrees, Z = 4, V = 3667.4(9) angstrom3; structure re fined to R(F) = 3.94% and R(wF) = 4.64% on 4680 data with F > 3sigma(F ). The Yb(III) is bonded to 5 in a tridentate manner, along with three nitrate ions. Crystallographic data for [Yb(5)2(NO3)2+] [(NO3)2(H2O)2 (CH3CN)2.52-]: C67H65.5N7.5O17P4Yb, triclinic, spacegroup P1BAR, a = 1 4.328(3) angstrom, b = 16.033(3) angstrom, c = 17.001(3) angstrom, a = 99.27(3)-degrees, beta = 101.92(3)-degrees, gamma = 107.36(3)-degrees , Z = 2, V = 3542(1) angstrom3; structure refined to R(F) = 5.64% and R(wF) = 7.32% on 10 711 data with F > 3sigma(F). The Yb is bonded to 5 in a tridentate fashion, along with one nitrate ion. Crystallographic data for [Th(5)2(NO3)22+][(NO3)2(H20)22-]: C62H54N6O20P4Th, monoclini c, spacegroup P2(1)/n, a = 19.136(4) angstrom, b = 18.365(4) angstrom, c = 21.448(4) angstrom, beta = 109.48(3)-degrees, Z = 4, V = 7106(3) angstrom3; structure refined to R(F) = 8.52% and R(wF) = 9.18% on 3518 data with F > 4sigma(F). Two tridentate ligands 5 and two nitrate ion s are bonded to Th(IV). This coordination chemistry is compared with t hat displayed by the bifunctional ligand, 2-[(C6H5)2P(O)]C5H4NO.