RESUMEN
In a search for more hydrocarbon solvent soluble derivatives of the parent ligand, 2,6-[Ph(2)P(O)CH(2)](2)C(5)H(3)NO (1a), a series of new ligands, 2,6-[R(2)P(O)CH(2)](2)C(5)H(3)NO [R = Bz (1b); Tol (1c); Et (1d); Pr (1e); Bu (1f); Pn (1g); Hx (1h); Hp (1i); and Oct (1j)] and 2,6-[RR'P(O)CH(2)](2)C(5)H(3)NO [R = Ph, R' = Bz (2a); R = Ph, R' = Me (2b); R = Ph, R' = Hx (2c); R = Ph, R' = Oct (2d)], have been prepared by either Arbusov or Grignard substitutions on 2,6-bis(chloromethyl)pyridine followed by N-oxidation. The new ligands have been characterized by spectroscopic methods, and their coordination chemistry with selected lanthanide ions has been surveyed. Several 1:1 and 2:1 ligand/metal complexes have been isolated, and single-crystal X-ray diffraction analyses for Nd(2a)(NO(3))(3), Er(2a)(NO(3))(3), Yb(1d)(NO(3))(3), and [Nd(1c)(2)](NO(3))(3) are described. The new structural data are discussed in relation to the structures of complexes formed by 1a.
RESUMEN
The trifunctional ligand 2,6-[(C6H5)2P(O)CH2]2 C5H3NO (1), in a mixed EtOH/MeOH solvent system, when combined with an aqueous nitric acid solution of Pu(IV), produces a 2:1 coordination complex, [Pu(1)2(NO3)2](NO3)2. A single crystal of [Pu(NO3)2(2,6-[(C6H5)2P(O)CH2]2C5H3NO)2](NO3)2x1.5H2Ox0.5MeOH was characterized by X-ray diffraction analysis. The crystal is monoclinic, space group P2(1)/n, with a = 19.1011(9) A, b = 18.2873(9) A, c = 21.507(1) A, alpha = gamma = 90 degrees, beta = 108.64(1) degrees, and Z = 4. Two neutral ligands (1) are bonded to the Pu(IV) ion in a tridentate fashion. Two nitrate ions also occupy inner sphere coordination positions, while two additional NO3- ions reside in the outer sphere. Comparison of the solution optical absorbance and solid diffuse reflectance spectra shows the same Pu(IV) chromophore exists in both solid and solution states.
RESUMEN
4-(Dihydroxyboryl)-3-nitrobenzoic acid, C7H6BNO6, M(r) = 210.94, monoclinic, P2(1)/n, a = 10.542 (2), b = 6.411 (1), c = 13.105 (4) A, beta = 106.47 (2) degrees, V = 849.3 (4) A3, Z = 4, Dm = 1.65 (flotation in CCl4/1,2-dibromoethane), Dx = 1.649 Mg m-3, lambda(Mo K alpha) = 0.71073 A, mu = 0.135 mm-1, F(000) = 432, T = 293 K, R = 0.0530 for 1328 observed reflections with F > 2 sigma(F). The molecule is flat [the carboxy and nitro groups are rotated 5.8 (4) and 1.9 (4) degrees, respectively, out of the plane] with the boronic acid group almost normal to the plane of the benzene ring, 92.4 (3) degrees. The B atom and one O atom of the nitro group are separated by only 2.457 (4) A implying an interaction that is consistent with observed chemical behavior.
Asunto(s)
Ácidos Borónicos/química , Estructura Molecular , Difracción de Rayos XRESUMEN
1-Bromoestra-1,3,5(10)-trien-3,17 beta-diol, C18H23BrO2, Mr = 351.3, orthorhombic, P2(1)2(1)2(1), a = 9.3864 (12), b = 12.927 (2), c = 12.948 (2) A, V = 1571.1 (4) A3, Z = 4, Dx = 1.484 Mg m-3, lambda(Mo K alpha) = 0.71069 A, mu = 259 mm-1, F(000) = 728, T = 298 K, R = 0.0514 for 2083 observed reflections. 1-Fluoroestra-1,3,5(10)-trien-3,17 beta-diol.0.5H2O, C18-H23FO2.0.5H2O, Mr = 299.4, orthorhombic, P2(1)2(1)2, a = 12.046 (4), b = 19.358 (5), c = 6.656 (2) A, V = 1552.1 (7) A3, Z = 4, Dx = 1.28 Mg m-3, lambda(Mo K alpha) = 0.71069 A, mu = 86 mm-1, F(000) = 644, T = 293 K, R = 0.0776 for 2781 observed reflections. Except for the carbon-halogen bond, bond angles and bond lengths of 1-bromoestradiol are within 7 e.s.d.'s of estradiol. Bond angles and bond lengths of 1-fluoroestradiol are within 11 and 7 e.s.d.'s of estradiol, respectively. The molecular conformations are nearly identical to that of estradiol. Like estradiol, 1-fluoroestradiol is present as a hemihydrate and extensive hydrogen bonding is observed. 1-Bromoestradiol is not hydrated and hydrogen bonding is limited to hydroxyl groups along the c axis.
