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• W2105816135 abstract "The NO2S2-donor macrocycle (L1) was synthesised from the ring closure reaction between Boc-N-protected 2,2′-iminobis(ethanethiol) (3) and 2,2′-(ethylenedioxy)bis(benzyl chloride) (4) followed by deprotection of the Boc-group. α,α′-Dibromo-p-xylene was employed as a dialkylating agent to bridge two L1 to yield the corresponding N-linked product (L2). The X-ray structure of L2 (as its HBr salt) is described. A range of Cd(II) and Hg(II) complexes of L1 (6–9) and L2 (10–12) were prepared and characterised. Reaction of HgX2 (X = Br or I) with L1 afforded [Hg(L1)Br]2[Hg2Br6]·2CH2Cl26 and [Hg(L1)I2] 7, respectively. For 6, the Hg(II) ion in the complex cation has a distorted tetrahedral coordination environment composed of S2N donor atoms from L1 and a bromo ligand. In 7 the coordination geometry is highly distorted tetrahedral, with the macrocycle coordinating in an exodentate manner via one S and one N atom. The remaining two coordination sites are occupied by iodide ions. [Hg(L1)(ClO4)]ClO48 was isolated from the reaction of Hg(ClO4)2 and L1. The X-ray structure reveals that all macrocyclic ring donors bind to the central mercury ion in this case, with the latter exhibiting a highly distorted octahedral coordination geometry. The O2S2-donors from the macrocyclic ring define the equatorial plane while the axial positions are occupied by the ring nitrogen as well as by an oxygen from a monodentate perchlorato ion. Reaction of Cd(NO3)2·4H2O with L1 afforded [Cd(L1)(NO3)2]·0.5CH2Cl29 in which L1 acts as a tridentate ligand, binding exo-fashion via its S2N donors. The remaining coordination positions are filled by two bidentate nitrate ions such that, overall, the cadmium is seven-coordinate. Reactions of HgX2 (X = Br or I) with L2 yielded the isostructural 2 : 1 (metal : ligand) complexes, [Hg2(L2)Br4] 10 and [Hg2(L2)I4] 11. Each mercury ion has a distorted tetrahedral environment made up of S and N donors from an exodentate L2 and two coordinated halides. Contrasting with this, the reaction of L2 with Cd(NO3)2·4H2O yielded a 1-D coordination network, {[Cd2(L2)(NO3)4]·2CH2Cl2}n12 in which each ring of L2 is exo-coordinated via two S atoms and one N atom to a cadmium ion which is also bound to one monodentate and one bidentate nitrate anion. The latter also has one of its oxygen atom attached to a neighboring cadmium via a nitroso (µ2-O) bridge such that the overall coordination geometry about each cadmium is seven-coordinate. The [Cd(L2)0.5(NO3)2] units are linked by an inversion to yield the polymeric arrangement." @default.
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• W2105816135 date "2005-01-01" @default.
• W2105816135 modified "2023-10-16" @default.
• W2105816135 title "Cadmium(ii) and mercury(ii) complexes of an NO2S2-donor macrocycle and its ditopic xylyl-bridged analogue" @default.
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• W2105816135 doi "https://doi.org/10.1039/b415794j" @default.
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