4.5 Article

Reactions of Cd(OAc)2•2H2O with variously substituted pyridines. Efforts to unravel the factors that determine structure/nuclearity of the products

Journal

POLYHEDRON
Volume 98, Issue -, Pages 238-250

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2015.06.002

Keywords

Cd(OAc)(2)center dot 2H(2)O; Lewis base; Coordination polymers; CPMAS Cd-113 NMR; Pzc species

Funding

  1. University of Delhi, Delhi
  2. Council of Scientific and Industrial Research

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The reactions of Cd(OAc)(2)center dot 2H(2)O with variously substituted pyridines in methanol afforded unique one-dimensional coordination polymers (1D CPs), [Cd-2(mu(2)-kappa(2):kappa(1)-OAc)(2)(mu(2)-kappa(1):kappa(1)-OAc)(2)L-2] (L= NC5H5 (1), NC5H4Me-3 (2), and NC5H3Me2-3,5 (3)) and [Cd-3(mu(3)-kappa(1):kappa(2)-OAc)(3)(mu(2)-kappa(2):kappa(1)-OAc)(2)(NC5H3Me2-3,4)(2)] (4), and discrete and bimolecular complexes, [(Cd(OAc)(2)(NC5H3Me2-3,4)(2)(H2O)(2)] (5), [Cd(kappa 2-OAc)(2)(NC5H4Me-4)(2)(H2O)]center dot[Cd(kappa 2-OAc)(2)(H2O)(2))] (6), [Cd(kappa(2)-OAc)(2)L2L']center dot xH(2)O (x = 0, L' = H2O, L = NC5H4 (OMe)-4 (7); (NC5H4Bu)-Bu-t-4 (8); x = 2, L = L' = NC5H4(NMe2)-4 (9 center dot 2H(2)O)). The products were characterised by elemental analysis, IR, solution NMR (H-1 and C-13), solid-state CP-MAS C-13{H-1} and Cd-113 NMR, TGA/DTA analyses, and single crystal X-ray diffraction. Phase purity of 1-4 was verified by powder Xray diffraction (PXRD). Plausible mechanisms of formation of the products are proposed based on a point zero charge model. 4 represents the first cadmium containing 1D CP that possesses a tridentate bridging (mu(3)-kappa(1):kappa(2)) acetate coordination mode and 6 represents the first structurally characterised bimolecular cadmium(II) complex containing two different neutral cadmium(II) coordination species per formula unit. 9 center dot 2H(2)O was calcined at 500 degrees C to afford CdO as confirmed by PXRD and the morphology of CdO was studied by scanning electron microscopy. (C) 2015 Elsevier Ltd. All rights reserved.

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