RESUMEN
The title complexes, catena-poly[[[diaquadiethanolmanganese(II)]-mu-1,4-bis(diphenylphosphinoyl)butane-kappa(2)O:O'] dinitrate 1,4-bis(diphenylphosphinoyl)butane solvate], {[Mn(C(2)H(6)O)(2)(C(28)H(28)O(2)P(2))(H(2)O)(2)](NO(3))(2).C(28)H(28)O(2)P(2)}(n), (I), and catena-poly[[[diaquadiethanolcobalt(II)]-mu-1,4-bis(diphenylphosphinoyl)butane-kappa(2)O:O'] dinitrate 1,4-bis(diphenylphosphinoyl)butane solvate], {[Co(C(2)H(6)O)(2)(C(28)H(28)O(2)P(2))(H(2)O)(2)](NO(3))(2).C(28)H(28)O(2)P(2)}(n), (II), are isostructural and centrosymmetric, with the M(II) ions at centres of inversion. The coordination geometry is octahedral, with each metal ion coordinated by two trans ethanol molecules, two trans water molecules and two bridging 1,4-bis(diphenylphosphinoyl)butane ligands which link the coordination centres to form one-dimensional polymeric chains. Parallel chains are linked by hydrogen bonds to uncoordinated 1,4-bis(diphenylphosphinoyl)butane molecules, which are bisected by a centre of inversion. Further hydrogen bonds, weak C-H...O interactions to nitrate anions, and weak C-H...pi interactions serve to stabilize the structure. This study reports a development of the coordination chemistry of bis(diphenylphosphinoyl)alkanes, with the first reported structures of complexes of the first-row transition metals with 1,4-bis(diphenylphosphinoyl)butane.
RESUMEN
The structure of the title complex, [Cu(NO(3))(2)(C(27)H(26)O(2)P(2))](n), consists of polymeric chains formed by propane-1,3-diylbis(diphenylphosphine oxide) ligands bridging between metal centres. The Cu atom lies on a twofold rotation axis and a further symmetry centre bisects the bridging bisphosphine dioxide ligand. The CuO(6) coordination geometry is a distorted octahedron, with the bidentate chelating nitrate groups adopting a cis configuration.
RESUMEN
The reactions of lanthanide nitrates, Ln(NO(3))(3), with bis(diphenylphosphino)methane dioxide, Ph(2)P(O)CH(2)P(O)Ph(2) (L), lead to complexes with three distinct classes of structure. At low ratios of Ln:L (<1:1.5) in acetonitrile the ionic complexes [Ln(NO(3))(2)L(2)](+)[Ln(NO(3))(4)L](-) (Ln = Pr, Eu) have been isolated. When carried out with a 1:2 or higher ratio in ethanol the reaction yields Ln(NO(3))(3)L(2) (Ln = La,Ce) and [Ln(NO(3))(2)L(2)H(2)O](+)[NO(3)](-) (Ln = Nd, Gd, Ho). Geometrical isomerism is found for the cations [Ln(NO(3))(2)L(2)H(2)O](+) and is attributed to the extent of hydrogen bonding to the coordinated water. Ligand redistribution occurs on heating in the solid state giving yellow solids in all cases. Crystallization of these materials from ethanol or acetonitrile gives [Ln(NO(3))L(3)](2+).2[NO(3)](-), which have been structurally characterized for Ln = Gd and Yb. Electrospray mass spectra indicate that extensive ligand exchange reactions occur in solution.